Ion exchange reactor with particle traps for lithium extraction

ABSTRACT

The present invention relates to the extraction of lithium from liquid resources such as natural and synthetic brines, leachate solutions from clays and minerals, and recycled products. For the extraction of lithium from the liquid resources, an ion exchange reactor has a tank, ion exchange particles, particle traps, and provision to modulate pH of the liquid resource.

CROSS-REFERENCE

This application claims the benefit of U.S. Provisional PatentApplication Ser. No. 62/636,766, filed Feb. 28, 2018; which isincorporated herein by reference in its entirety.

BACKGROUND OF THE INVENTION

Lithium is an essential element for high-energy rechargeable batteriesand other technologies. Lithium can be found in a variety of liquidsolutions, including natural and synthetic brines and leachate solutionsfrom minerals and recycled products.

SUMMARY OF THE INVENTION

Lithium can be extracted from liquid resources using an ion exchangeprocess based on inorganic ion exchange materials. Inorganic ionexchange materials absorb lithium ions from a liquid resource whilereleasing hydrogen ions, and then elute lithium ions in acid whileabsorbing hydrogen ions. The ion exchange process can be repeated toextract lithium ions from a liquid resource and yield a concentratedlithium ion solution. The concentrated lithium ion solution can befurther processed into chemicals for the battery industry or otherindustries.

Ion exchange particles are loaded into an ion exchange reactor forlithium extraction. Alternating flows of brine, water, and acid areflowed through the ion exchange reactor to enable lithium uptake fromthe brine into the ion exchange particles, water washing of residualbrine from the ion exchange particles, and acid elution of lithium fromthe ion exchange particles to form a lithium eluate solution. Therelease of hydrogen during lithium uptake will acidify the brine andlimit lithium uptake unless the pH of the brine is maintained in asuitable range to facilitate thermodynamically favorable lithium uptakeand concomitant hydrogen release.

To retain the ion exchange particles in the ion exchange reactor, whileallowing flows of brine, water, and acid to enter and exit the ionexchange reactor, one or more particle traps are used with the ionexchange reactor. These particle traps separate the solid ion exchangeparticles from the liquid flows by utilizing filtration, gravitysedimentation, centrifugal sedimentation, magnetic fields, other methodsof solid-liquid separation, or combinations thereof.

One aspect described herein is an ion exchange reactor for generating alithium eluate solution from a liquid resource, comprising: a tank; ionexchange particles that selectively absorb lithium from said liquidresource and elute said lithium eluate solution when treated with anacid solution after absorbing lithium from said liquid resource; one ormore particle traps; and provision to modulate pH of said liquidresource.

In some embodiments, said tank has a conical shape. In some embodiments,said conical shape allows said ion exchange particles to settle into asettled bed so that liquid can be removed from above said settled bed.In some embodiments, modulation of said pH of said liquid resourceoccurs in the tank. In some embodiments, modulation of said pH of saidliquid resource occurs prior to injection of said liquid resource intothe tank. In some embodiments, said one or more particle traps compriseone or more filters inside said tank. In some embodiments, said one ormore particle traps is located at the bottom of said tank. In someembodiments, said one or more particle traps comprise one or moremeshes.

In some embodiments, said one or more meshes comprise a pore space ofless than about 200 microns. In some embodiments, said one or moremeshes comprise a pore space of less than about 100 microns. In someembodiments, said one or more meshes comprise a pore space of less thanabout 100 microns. In some embodiments, said one or more meshes comprisea pore space of less than about 50 microns. In some embodiments, saidone or more meshes comprise a pore space of less than about 25 microns.In some embodiments, said one or more meshes comprise a pore space ofless than about 10 microns.

In some embodiments, said one or more particle traps comprisemulti-layered meshes. In some embodiments, said multi-layered meshescomprise at least one finer mesh for filtration and at least one coarsermesh for structural support. In some embodiments, said one or moreparticle traps comprise one or more meshes supported by a structuralsupport. In some embodiments, said one or more particle traps compriseone or more polymer meshes. In some embodiments, said one or morepolymer meshes are selected from the group consisting ofpolyetheretherketone, ethylene tetrafluorethylene, polyethyleneterephthalate, polypropylene, and combinations thereof. In someembodiments, said one or more particle traps comprise one or more meshescomprising a metal wire mesh. In some embodiments, said metal wire meshis coated with a polymer.

In some embodiments, said ion exchange reactor is configured to movesaid ion exchange particles into one or more columns for washing. Insome embodiments, said ion exchange reactor is configured to allow theion exchange particles to settle into one or more columns for washing.In some embodiments, said columns are affixed to the bottom of saidtank. In some embodiments, said one or more particle traps comprise oneor more filters mounted in one or more ports through the wall of saidtank. In some embodiments, said one or more particle traps comprise oneor more filters external to said tank, and with provision for fluidcommunication between said one or more filters and said tank. In someembodiments, said one or more particle traps comprise one or moregravity sedimentation devices external to said tank, and with provisionfor fluid communication between said one or more gravity sedimentationdevices and said tank. In some embodiments, said one or more particletraps comprise one or more gravity sedimentation devices internal tosaid tank. In some embodiments, said one or more particle traps compriseone or more centrifugal sedimentation devices external to said tank, andwith provision for fluid communication between said one or morecentrifugal sedimentation devices and said tank.

In some embodiments, said one or more particle traps comprise one ormore centrifugal sedimentation devices internal to said tank. In someembodiments, said one or more particle traps comprise one or moresettling tanks, one or more centrifugal devices, or combinations thereofexternal to said tank, and with provision for fluid communicationbetween said one or more settling tanks, centrifugal devices, orcombinations thereof, and said tank. In some embodiments, said one ormore particle traps comprise one or more meshes, one or more centrifugaldevices, or combinations thereof external to said tank, and withprovision for fluid communication between said one or more meshes,centrifugal devices, or combinations thereof, and said tank. In someembodiments, said one or more particle traps comprise one or moresettling tanks, one or more meshes, or combinations thereof external tosaid tank, and with provision for fluid communication between said oneor more settling tanks, meshes, or combinations thereof, and said tank.In some embodiments, said one or more particle traps comprise one ormore meshes, one or more settling tanks, one or more centrifugaldevices, or combinations thereof external to said tank, and withprovision for fluid communication between said one or more meshes, oneor more settling tanks, centrifugal devices, or combinations thereof,and said tank.

In some embodiments, the ion exchange particles are stirred. In someembodiments, the ion exchange particles are stirred by a mixer. In someembodiments, the ion exchange particles are stirred by a propeller. Insome embodiments, the ion exchange particles are fluidized by pumpingsolution into the tank near the bottom of the tank. In some embodiments,the ion exchange particles are fluidized by pumping solution from thetank back into the tank near the bottom of the tank. In someembodiments, the ion exchange particles are fluidized by pumping aslurry of the ion exchange particles from near the bottom of the tank toa higher level in the tank.

In some embodiments, the ion exchange reactor further comprises one ormore staged elution tanks, wherein intermediate eluate solutionscomprising mixtures of protons and lithium ions are stored and usedfurther to elute lithium from said ion exchange particles that arefreshly lithiated. In some embodiments, the ion exchange reactor furthercomprises one or more staged elution tanks, wherein intermediate eluatesolutions comprising mixtures of protons and lithium ions are mixed withadditional acid and used further to elute lithium from said ion exchangeparticles.

In some embodiments, said ion exchange particles further comprise acoating material. In some embodiments, said coating material is apolymer. In some embodiments, said coating of said coating materialcomprises a chloro-polymer, a fluoro-polymer, a chloro-fluoro-polymer, ahydrophilic polymer, a hydrophobic polymer, co-polymers thereof,mixtures thereof, or combinations thereof.

One aspect described herein is an ion exchange system for generating alithium eluate solution from a liquid resource, comprising: a networkedplurality of tanks; ion exchange particles that selectively absorblithium from said liquid resource and elute said lithium eluate solutionwhen treated with an acid solution; one or more particle traps; andprovision to modulate pH of said liquid resource.

In some embodiments, said ion exchange particles are retained in saidnetworked plurality of tanks with flows of brine, washing solution, andacid alternately moving through said plurality of tanks. In someembodiments, said ion exchange particles are moved through saidnetworked plurality of tanks against counter-current flows of brine,washing solution, and acid. In some embodiments, tanks selected fromsaid networked plurality of tanks are sized for batches of brine,washing solution, or acid and wherein said ion exchange particles aremoved through said networked plurality of tanks.

One aspect described herein is a method of generating a lithium eluatesolution from a liquid resource, comprising: providing an ion exchangereactor comprising a tank, ion exchange particles that selectivelyabsorb lithium from a liquid resource and elute a lithium eluatesolution when treated with an acid solution after absorbing lithium ionsfrom said liquid resource, one or more particle traps, and provision tomodulate pH of said liquid resource; flowing a liquid resource into saidion exchange reactor thereby allowing said ion exchange particles toselectively absorb lithium from said liquid resource; treating said ionexchange particles with an acid solution to yield said lithium eluatesolution; and passing said lithium eluate solution through said one ormore particle traps to collect said lithium eluate solution.

In some embodiments, said tank has a conical shape. In some embodiments,said conical shape allows said ion exchange particles to settle into asettled bed so that liquid can be removed from above said settled bed.In some embodiments, modulation of said pH of said liquid resourceoccurs in the tank. In some embodiments, modulation of said pH of saidliquid resource occurs prior to injection of said liquid resource intothe tank. In some embodiments, said one or more particle traps compriseone or more filters inside said tank. In some embodiments, said one ormore particle traps is located at the bottom of said tank. In someembodiments, said one or more particle traps comprise one or moremeshes.

In some embodiments, said one or more meshes comprise a pore space ofless than about 200 microns. In some embodiments, said one or moremeshes comprise a pore space of less than about 100 microns. In someembodiments, said one or more meshes comprise a pore space of less thanabout 100 microns. In some embodiments, said one or more meshes comprisea pore space of less than about 50 microns. In some embodiments, saidone or more meshes comprise a pore space of less than about 25 microns.In some embodiments, said one or more meshes comprise a pore space ofless than about 10 microns. In some embodiments, said one or moreparticle traps comprise multi-layered meshes. In some embodiments, saidmulti-layered meshes comprise at least one finer mesh for filtration andat least one coarser mesh for structural support. In some embodiments,said one or more particle traps comprise one or more meshes supported bya structural support. In some embodiments, said one or more particletraps comprise one or more polymer meshes. In some embodiments, said oneor more polymer meshes are selected from the group consisting ofpolyetheretherketone, ethylene tetrafluorethylene, polyethyleneterephthalate, polypropylene, and combinations thereof. In someembodiments, said one or more particle traps comprise one or more meshescomprising a metal wire mesh. In some embodiments, said metal wire meshis coated with a polymer.

In some embodiments, said ion exchange reactor is configured to movesaid ion exchange particles into one or more columns for washing. Insome embodiments, said ion exchange reactor is configured to allow theion exchange particles to settle into one or more columns for washing.In some embodiments, said columns are affixed to the bottom of saidtank. In some embodiments, said one or more particle traps comprise oneor more filters mounted in one or more ports through the wall of saidtank.

In some embodiments, said one or more particle traps comprise one ormore filters external to said tank, and with provision for fluidcommunication between said one or more filters and said tank. In someembodiments, said one or more particle traps comprise one or moregravity sedimentation devices external to said tank, and with provisionfor fluid communication between said one or more gravity sedimentationdevices and said tank. In some embodiments, said one or more particletraps comprise one or more gravity sedimentation devices internal tosaid tank. In some embodiments, said one or more particle traps compriseone or more centrifugal sedimentation devices external to said tank, andwith provision for fluid communication between said one or morecentrifugal sedimentation devices and said tank. In some embodiments,said one or more particle traps comprise one or more centrifugalsedimentation devices internal to said tank. In some embodiments, saidone or more particle traps comprise one or more settling tanks, one ormore centrifugal devices, or combinations thereof external to said tank,and with provision for fluid communication between said one or moresettling tanks, centrifugal devices, or combinations thereof, and saidtank. In some embodiments, said one or more particle traps comprise oneor more meshes, one or more centrifugal devices, or combinations thereofexternal to said tank, and with provision for fluid communicationbetween said one or more meshes, centrifugal devices, or combinationsthereof, and said tank. In some embodiments, said one or more particletraps comprise one or more settling tanks, one or more meshes, orcombinations thereof external to said tank, and with provision for fluidcommunication between said one or more settling tanks, meshes, orcombinations thereof, and said tank. In some embodiments, said one ormore particle traps comprise one or more meshes, one or more settlingtanks, one or more centrifugal devices, or combinations thereof externalto said tank, and with provision for fluid communication between saidone or more meshes, one or more settling tanks, centrifugal devices, orcombinations thereof, and said tank.

In some embodiments, the ion exchange particles are stirred. In someembodiments, the ion exchange particles are stirred by a mixer. In someembodiments, the ion exchange particles are stirred by a propeller. Insome embodiments, the ion exchange particles are fluidized by pumpingsolution into the tank near the bottom of the tank. In some embodiments,the ion exchange particles are fluidized by pumping solution from thetank back into the tank near the bottom of the tank. In someembodiments, the ion exchange particles are fluidized by pumping aslurry of the ion exchange particles from near the bottom of the tank toa higher level in the tank.

In some embodiments, the method further comprises one or more stagedelution tanks, wherein intermediate eluate solutions comprising mixturesof protons and lithium ions are stored and used further to elute lithiumfrom said ion exchange particles that are freshly lithiated. In someembodiments, the method further comprises one or more staged elutiontanks, wherein intermediate eluate solutions comprising mixtures ofprotons and lithium ions are mixed with additional acid and used furtherto elute lithium from said ion exchange particles.

In some embodiments, said ion exchange particles further comprise acoating material. In some embodiments, said coating material is apolymer. In some embodiments, said coating material comprises achloro-polymer, a fluoro-polymer, a chloro-fluoro-polymer, a hydrophilicpolymer, a hydrophobic polymer, co-polymers thereof, mixtures thereof,or combinations thereof.

One aspect described herein is an ion exchange reactor for generating alithium eluate solution from a liquid resource, comprising: a tank witha conical shape, wherein said conical shape allows said ion exchangeparticles to settle into a settled bed so that liquid can be removedfrom above said settled bed; ion exchange particles that selectivelyabsorb lithium from said liquid resource and elute said lithium eluatesolution when treated with an acid solution after absorbing lithium fromsaid liquid resource; one or more particle traps located at the bottomof said tank, wherein said one or more particle traps comprise one ormore meshes; and provision to modulate pH of said liquid resource,wherein said modulation of said pH of said liquid resource is configuredto occur in the tank or prior to injection of said liquid resource intothe tank.

In some embodiments, said one or more meshes comprise a pore space ofless than about 200 microns. In some embodiments, said one or moremeshes comprise a pore space of less than about 100 microns. In someembodiments, said one or more meshes comprise a pore space of less thanabout 100 microns. In some embodiments, said one or more meshes comprisea pore space of less than about 50 microns. In some embodiments, saidone or more meshes comprise a pore space of less than about 25 microns.In some embodiments, said one or more meshes comprise a pore space ofless than about 10 microns.

In some embodiments, said one or more meshes are one or more polymermeshes. In some embodiments, said one or more polymer meshes areselected from the group consisting of polyetheretherketone, ethylenetetrafluorethylene, polyethylene terephthalate, polypropylene, andcombinations thereof. In some embodiments, said one or more meshescomprise a metal wire mesh In some embodiments, said metal wire mesh iscoated with a polymer. In some embodiments, said polymer coating saidmetal wire mesh is selected from the group consisting ofpolyetheretherketone, ethylene tetrafluorethylene, polyethyleneterephthalate, polypropylene, and combinations thereof.

One aspect described herein is an ion exchange reactor for generating alithium eluate solution from a liquid resource, comprising: a tank witha conical shape, wherein said conical shape allows said ion exchangeparticles to settle into a settled bed so that liquid can be removedfrom above said settled bed; ion exchange particles that selectivelyabsorb lithium from said liquid resource and elute said lithium eluatesolution when treated with an acid solution after absorbing lithium fromsaid liquid resource; one or more particle traps located at the bottomof said tank, wherein said one or more particle traps comprisemulti-layered meshes; and provision to modulate pH of said liquidresource, wherein said modulation of said pH of said liquid resource isconfigured to occur in the tank or prior to injection of said liquidresource into the tank.

In some embodiments, said multi-layered meshes comprise at least onefiner mesh for filtration and at least one coarser mesh for structuralsupport. In some embodiments, said one or more particle traps compriseone or more meshes supported by a structural support. In someembodiments, said one or more meshes are one or more polymer meshes. Insome embodiments, said one or more polymer meshes are selected from thegroup consisting of polyetheretherketone, ethylene tetrafluorethylene,polyethylene terephthalate, polypropylene, and combinations thereof. Insome embodiments, said one or more meshes comprise a metal wire mesh. Insome embodiments, said metal wire mesh is coated with a polymer. In someembodiments, said polymer coating said metal wire mesh is selected fromthe group consisting of polyetheretherketone, ethylenetetrafluorethylene, polyethylene terephthalate, polypropylene, andcombinations thereof.

One aspect described herein is a method of generating a lithium eluatesolution from a liquid resource, comprising: providing an ion exchangereactor comprising (i) a tank with a conical shape, wherein said conicalshape allows said ion exchange particles to settle into a settled bed sothat liquid can be removed from above said settled bed; (ii) ionexchange particles that selectively absorb lithium from said liquidresource and elute said lithium eluate solution when treated with anacid solution after absorbing lithium from said liquid resource; (iii)one or more particle traps located at the bottom of said tank, whereinsaid one or more particle traps comprise one or more meshes; and (iv)provision to modulate pH of said liquid resource, wherein saidmodulation of said pH of said liquid resource is configured to occur inthe tank or prior to injection of said liquid resource into the tank;flowing a liquid resource into said ion exchange reactor therebyallowing said ion exchange particles to selectively absorb lithium fromsaid liquid resource; treating said ion exchange particles with an acidsolution to yield said lithium eluate solution; and passing said lithiumeluate solution through said one or more particle traps to collect saidlithium eluate solution.

In some embodiments, said one or more meshes comprise a pore space ofless than about 200 microns. In some embodiments, said one or moremeshes comprise a pore space of less than about 100 microns. In someembodiments, said one or more meshes comprise a pore space of less thanabout 100 microns. In some embodiments, said one or more meshes comprisea pore space of less than about 50 microns. In some embodiments, saidone or more meshes comprise a pore space of less than about 25 microns.In some embodiments, said one or more meshes comprise a pore space ofless than about 10 microns.

In some embodiments, said one or more meshes are one or more polymermeshes. In some embodiments, one or more polymer meshes are selectedfrom the group consisting of polyetheretherketone, ethylenetetrafluorethylene, polyethylene terephthalate, polypropylene, andcombinations thereof. In some embodiments, said one or more meshescomprise a metal wire mesh In some embodiments, said metal wire mesh iscoated with a polymer. In some embodiments, said polymer coating saidmetal wire mesh is selected from the group consisting ofpolyetheretherketone, ethylene tetrafluorethylene, polyethyleneterephthalate, polypropylene, and combinations thereof.

One aspect described herein is a method of generating a lithium eluatesolution from a liquid resource, comprising: providing an ion exchangereactor comprising: (i) a tank with a conical shape, wherein saidconical shape allows said ion exchange particles to settle into asettled bed so that liquid can be removed from above said settled bed;(ii) ion exchange particles that selectively absorb lithium from saidliquid resource and elute said lithium eluate solution when treated withan acid solution after absorbing lithium from said liquid resource;(iii) one or more particle traps located at the bottom of said tank,wherein said one or more particle traps comprise multi-layered meshes;and (iv) provision to modulate pH of said liquid resource, wherein saidmodulation of said pH of said liquid resource is configured to occur inthe tank or prior to injection of said liquid resource into the tank;flowing a liquid resource into said ion exchange reactor therebyallowing said ion exchange particles to selectively absorb lithium fromsaid liquid resource; treating said ion exchange particles with an acidsolution to yield said lithium eluate solution; and passing said lithiumeluate solution through said one or more particle traps to collect saidlithium eluate solution.

In some embodiments, said multi-layered meshes comprise at least onefiner mesh for filtration and at least one coarser mesh for structuralsupport. In some embodiments, said one or more particle traps compriseone or more meshes supported by a structural support. In someembodiments, said one or more meshes are one or more polymer meshes. Insome embodiments, said one or more polymer meshes are selected from thegroup consisting of polyetheretherketone, ethylene tetrafluorethylene,polyethylene terephthalate, polypropylene, and combinations thereof.

In some embodiments, said one or more meshes comprise a metal wire mesh.In some embodiments, said metal wire mesh is coated with a polymer. Insome embodiments, said polymer coating said metal wire mesh is selectedfrom the group consisting of polyetheretherketone, ethylenetetrafluorethylene, polyethylene terephthalate, polypropylene, andcombinations thereof.

INCORPORATION BY REFERENCE

All publications, patents, and patent applications mentioned in thisspecification are herein incorporated by reference to the same extent asif each individual publication, patent, or patent application wasspecifically and individually indicated to be incorporated by reference.

BRIEF DESCRIPTION OF THE DRAWINGS

The novel features of the invention are set forth with particularity inthe appended claims. A better understanding of the features andadvantages of the present invention will be obtained by reference to thefollowing detailed description that sets forth illustrative embodiments,in which the principles of the invention are utilized, and theaccompanying drawings of which:

FIG. 1 illustrates an ion exchange reactor comprising a stirred tankhaving a conical shape and one or more filters mounted in a port throughthe wall of the tank.

FIG. 2 illustrates an ion exchange reactor comprising a stirred tankhaving a conical shape and one or more filters inside the tank.

FIG. 3 illustrates an ion exchange reactor comprising a stirred tankhaving a conical shape and one or more filters external to the tank,with provision for fluid communication between the one or more filtersand tank.

FIG. 4 illustrates an ion exchange reactor comprising a stirred tank andan external conical-shaped settling tank, with provision for fluidcommunication between the settling tank and the tank.

FIG. 5 illustrates an ion exchange system comprising a networkedplurality of stirred tanks, and one or more filters external to thetanks.

FIG. 6 illustrates an ion exchange system comprising a networkedplurality of tanks including multiple brine reactors networked with oneacid reactor.

FIG. 7 illustrates an ion exchange system comprising a networkedplurality of tanks where ion exchange particles move against acountercurrent flow of brine, washing solution, and acid and the systemis configured to operate continuously or semi-continuously.

FIG. 8 illustrates an ion exchange reactor with provision for a seriesof staged elution tanks, wherein intermediate eluate solutionscomprising a mixture of protons and lithium ions are stored and usedfurther to elute lithium from the ion exchange particles.

FIG. 9A illustrates an ion exchange reactor comprising a stirred tankhaving a partial conical shape and one or more filters inside the tank.

FIG. 9B depicts lithium recovery from a liquid resource over multiplecycles between the liquid resource and acid using the ion exchangereactor illustrated in FIG. 9A.

FIG. 10 illustrates an ion exchange reactor comprising a stirred tankhaving a partial conical shape ending in a thinner cylindrical columnwith one or more filters inside the tank.

FIG. 11 illustrates and ion exchange reactor comprising a stirred tankhaving a partial conical shape ending in a thinner cylindrical columnwith one or more filters inside the tank and a pumping unit to pumpliquid out of the tank and back into the bottom of the thinnercylindrical column.

FIG. 12 illustrates an ion exchange reactor comprising a stirred tankhaving a partial conical shape with one or more filters inside the tankand a pumping unit to pump liquid out of the tank and back into thebottom of the thinner cylindrical column.

DETAILED DESCRIPTION OF THE INVENTION

The terms “lithium”, “lithium ion”, and “Li^(t)” are usedinterchangeably in the present specification and these terms aresynonymous unless specifically noted to the contrary. The terms“hydrogen”, “hydrogen ion”, “proton”, and “H⁺” are used interchangeablyin the present specification and these terms are synonymous unlessspecifically noted to the contrary. The terms “lithiated”,“lithium-enriched”, and “lithium-exchanged” are used interchangeably inthe present specification and these terms are synonymous unlessspecifically noted to the contrary. The terms “protonated”,“hydrogen-enriched”, and “proton-exchanged”, are used interchangeably inthe present specification and these terms are synonymous unlessspecifically noted to the contrary.

Lithium Ion Exchange Reactor with Particle Traps

An aspect of the invention described herein is an ion exchange reactorfor extracting lithium from a liquid resource. This reactor functions tocontact the liquid resource with ion exchange particles so that the ionexchange particles can uptake lithium from the liquid resource, separatethe ion exchange particles from the liquid resource, wash the particleswith aqueous solution, separate the ion exchange particles from theaqueous solution, elute lithium out of the particles using an acidsolution, and separate the particles from the acid solution. The reactorincludes a provision for measuring and adjusting the pH of the liquidresource, to neutralize protons released by the ion exchange materialduring lithium uptake.

An aspect of the invention described herein is an ion exchange reactorfor extracting lithium from a liquid resource, comprising: a) one ormore tanks; b) ion exchange particles; c) one or more particle traps;and d) provision to modulate pH of the liquid resource.

An aspect of the invention described herein is a method for extractinglithium from a liquid resource, comprising: a) providing an ion exchangereactor comprising one or more particle traps; b) providing ion exchangeparticles in said ion exchange reactor; c) contacting said ion exchangeparticles in said ion exchange reactor with said liquid resource,wherein hydrogen ions from said ion exchange particles are exchangedwith lithium ions from said liquid resource to produce lithium-enrichedion exchange particles in said ion exchange unit; d) removing saidliquid resource from said ion exchange reactor while retaining said ionexchange particles in said ion exchange reactor using said one or moreparticle traps; e) washing said lithium-enriched ion exchange particleswith a water solution one or more times; f) removing said water solutionfrom said ion exchange reactor while retaining said ion exchangeparticles in said ion exchange reactor using said one or more particletraps; g) treating said lithium-enriched ion exchange particles with anacid solution, wherein said lithium ions from said lithium-enriched ionexchange particles are exchanged with hydrogen ions from said acidsolution to produce a lithium eluate; and h) removing said lithiumeluate from said ion exchange reactor while retaining said ion exchangeparticles in said ion exchange reactor using said one or more particletraps.

In some embodiments, the acid solution is hydrochloric acid, sulfuricacid, nitric acid, other acid, or combinations thereof. In someembodiments, the acid solution has a proton concentration less thanabout 10 N, less than about 3N, less than about 1N, less than about 0.3N, less than about 0.1 N, more than about 0.05 N, more than about 0.1 N,more than about 0.2 N, more than about 0.3 N, more than about 0.4 N,more than about 0.5 N, more than about 0.75 N, more than about 1 N, morethan about 2 N, more than about 3 N, more than about 4 N, more thanabout 5 N, more than about 6 N, more than about 7 N, more than about 8N, more than about 9 N, from about 0.05 N to about 10 N, from about 0.1N to about 10 N, from about 0.2 N to about 10 N, from about 0.3 N toabout 10 N, from about 0.4 N to about 10 N, from about 0.5 N to about 10N, from about 0.6 N to about 10 N, from about 0.7 N to about 10 N, fromabout 0.8 N to about 10 N, from about 0.9 N to about 10 N, from about 1N to about 10 N, from about 1 N to about 9 N, from about 2 N to about 8N, or from about 3 N to about 7 N.

In some embodiments, the lithium eluate solution contains lithiumchloride, lithium sulfate, lithium nitrate, or other lithium salts. Insome embodiments, the lithium eluate solution is processed to producelithium metal, lithium carbonate, lithium hydroxide, lithium hydroxidemonohydrate, lithium nitrate, lithium phosphate, lithium chloride,lithium metal, organometallic lithium, or other lithium salts.

Shaped Tanks

An aspect of the invention described herein is an ion exchange reactorfor extracting lithium from liquid resources, comprising: a) a tank witha cross sectional area that is smaller at the bottom; b) ion exchangeparticles that are loaded into the tank; c) one or more particle trapsfor containing the ion exchange particles in the tank while liquid flowsare removed from the tank; and d) a provision for pH modulation of theliquid resource in the tank.

An aspect of the invention described herein is an ion exchange reactorfor generating a lithium eluate solution from a liquid resource,comprising: a tank with a conical shape, wherein said conical shapeallows said ion exchange particles to settle into a settled bed so thatliquid can be removed from above said settled bed; ion exchangeparticles that selectively absorb lithium from said liquid resource andelute said lithium eluate solution when treated with an acid solutionafter absorbing lithium from said liquid resource; one or more particletraps located at the bottom of said tank, wherein said one or moreparticle traps comprise one or more meshes; and provision to modulate pHof said liquid resource, wherein said modulation of said pH of saidliquid resource is configured to occur in the tank or prior to injectionof said liquid resource into the tank.

An aspect of the invention described herein is an ion exchange reactorfor generating a lithium eluate solution from a liquid resource,comprising: a tank with a conical shape, wherein said conical shapeallows said ion exchange particles to settle into a settled bed so thatliquid can be removed from above said settled bed; ion exchangeparticles that selectively absorb lithium from said liquid resource andelute said lithium eluate solution when treated with an acid solutionafter absorbing lithium from said liquid resource; one or more particletraps located at the bottom of said tank, wherein said one or moreparticle traps comprise multi-layered meshes; and provision to modulatepH of said liquid resource, wherein said modulation of said pH of saidliquid resource is configured to occur in the tank or prior to injectionof said liquid resource into the tank.

In some embodiments, the ion exchange reactor comprises a tank with acone shape. In some embodiments, the cone shape allows the ion exchangeparticles to settle to the bottom of the cone shape while liquid isremoved from the tank above the settled bed of ion exchange particles.In some embodiments, a particle trap may have an inlet located above thesettled height of the ion exchange particles. In some embodiments, theshape of the tank enables removal of liquid from above the settled bedof ion exchange particles. In some embodiments, a port is located at thebottom or near the bottom of the tank to allow a slurry comprising ionexchange particles and water to be removed from the tank or injectedinto the tank. In some embodiments, a filter is located at the bottom ornear the bottom of the tank that allows a slurry comprising ion exchangeparticles and water to be dewatered. In some embodiments, a filter islocated at the bottom or near the bottom of the tank that allowssolutions to be injected into the tank through the filter. In someembodiments, the ion exchange reactor comprises a tank that is conicalor pyramidal near the bottom. In some embodiments, the ion exchangereactor comprises a tank that is conical or pyramidal near the bottomand cylindrical or rectangular near the top.

In some embodiments, volumes of liquid resource and acid solution areloaded into the ion exchange reactor. In some embodiments, the volume ofthe liquid resource loaded into the ion exchange reactor is greater thanthe volume of the acid solution by a factor of more than about 2×, morethan about 5×, more than about 10×, more than about 20×, more than about50×, or more than about 100×. In some embodiments, the reactor tank mayhave a cone shape that is narrower at the bottom to facilitate mixing ofion exchange particles in the tank, to facilitate settling of the ionexchange particles, to facilitate washing of the ion exchange particles,or to facilitate separation of the ion exchange particles from liquidsolutions such as liquid resource, acid solution, or washing solution.

In some embodiments, the ion exchange reactor may have a mixing devicefor mixing ion exchange particles with liquid resources, washingsolutions, or acid elution solutions. In some embodiments, the mixingdevice is an overhead mixer. In some embodiments, the mixing device is apropeller that circulates brine throughout the tank. In someembodiments, the mixing device is a propeller that lifts a slurry of ionexchange particles off the bottom of the tank. In some embodiments, theion exchange reactor may have one or more mixing devices. In someembodiments, the mixing device is a pump that injects solution into thetank, thereby agitating a bed of ion exchange particles. In someembodiments, the mixing device is a pump that injects solution into thetank, thereby fluidizing or suspending ion exchange particles insolution. In some embodiments, the ion exchange particles are mixed in asolution by pumping a slurry from near the bottom of the tank andinjecting said slurry into a higher level of the tank. In someembodiments, the fluidized ion exchange material is mixed by pumping itinto and/or out of the tank with no filtration. In some embodiments, thetank of the ion exchange reactor is fitted with one or more sprayersthat wash the ion exchange particles off the sides of the tank and movethem to the bottom of the tank. In some embodiments, the ion exchangereactor is equipped with baffles. In some embodiments, one or more tanksare equipped with baffles. In some embodiments, one or more tanks areequipped with baffles to improve mixing of the ion exchange particleswith brine, water, acid, or other solutions.

In some embodiments, the tank of the ion exchange reactor isrectangular, cylindrical, conical, spherical, parallelogram,rhombohedral, pyramidal, or combinations thereof.

In some embodiments, the one or more meshes comprise a pore space ofless than about 200 microns. In some embodiments, the one or more meshescomprise a pore space of less than about 100 microns. In someembodiments, the one or more meshes comprise a pore space of less thanabout 100 microns. In some embodiments, the one or more meshes comprisea pore space of less than about 50 microns. In some embodiments, the oneor more meshes comprise a pore space of less than about 25 microns. Insome embodiments, the one or more meshes comprise a pore space of lessthan about 10 microns. In some embodiments, the one or more meshes areone or more polymer meshes. In some embodiments, the one or more polymermeshes are selected from the group consisting of polyetheretherketone,ethylene tetrafluorethylene, polyethylene terephthalate, polypropylene,and combinations thereof. In some embodiments, the one or more meshescomprise a metal wire mesh. In some embodiments, the metal wire mesh iscoated with a polymer. In some embodiments, the polymer coating saidmetal wire mesh is selected from the group consisting ofpolyetheretherketone, ethylene tetrafluorethylene, polyethyleneterephthalate, polypropylene, and combinations thereof.

In some embodiments, the multi-layered meshes comprise at least onefiner mesh for filtration and at least one coarser mesh for structuralsupport. In some embodiments, the one or more particle traps compriseone or more meshes supported by a structural support. In someembodiments, the one or more meshes are one or more polymer meshes. Insome embodiments, the one or more polymer meshes are selected from thegroup consisting of polyetheretherketone, ethylene tetrafluorethylene,polyethylene terephthalate, polypropylene, and combinations thereof. Insome embodiments, the one or more meshes comprise a metal wire mesh. Insome embodiments, the metal wire mesh is coated with a polymer. In someembodiments, the polymer coating said metal wire mesh is selected fromthe group consisting of polyetheretherketone, ethylenetetrafluorethylene, polyethylene terephthalate, polypropylene, andcombinations thereof.

Filters

In some embodiments, the particle trap is a filter. In some embodiments,the filter is operated as a cake filter. In some embodiments, the filteris operated to limit formation of a filter cake. In some embodiments,the filter is operated with sheer flow. In some embodiments, the filteris operated with backwashing.

In some embodiments, the filter comprises a polymer, a porous polymer, apolymer mesh, or a polymer composite. In some embodiments, the filtercomprises a woven polymer or a polymer fabric. In some embodiments, thefilter is comprised of polypropylene, polyetheretherketone (PEEK),polyvinylidene difluoride (PVDF), polysulfone, polyethylene, nylon, oranother polymer material. In some embodiments, the filter comprises aceramic, metal, or alloy material. In some embodiments, the filtercomprises a polymer, polyaryl ether ketone, polyethylene terephthalate,ethylene tetrafluoroethylene, a hydrophilic polymer, a hydrophobicpolymer, a co-polymer, a block-copolymer, or combinations thereof. Insome embodiments, the filter comprises a steel or other metallic meshcoated with polymer. In some embodiments, the filter comprises astainless steel mesh coated with polymer. In some embodiments, thefilter comprises a 304 stainless steel mesh coated with polymer. In someembodiments, the coating on the steel mesh comprises an epoxy, asilicone, a chloro-polymer, a fluor-polymer, a chloro-fluoro-polymer,polypropylene, polyetheretherketone (PEEK), polyvinylidene difluoride(PVDF), polysulfone, polyethylene, a thermal cure epoxy, an air dryepoxy, a phenolic epoxy, a phenolic polymer, polytetrafluoroethylene,fluorinated ethylene propylene, a ceramic-epoxy composite coating,ethylene chlorotrifluoroethylene, other polymers combinations thereof,or copolymers thereof. In some embodiments, the mesh comprises an epoxy,a silicone, a chloro-polymer, a fluor-polymer, a chloro-fluoro-polymer,polypropylene, polyetheretherketone (PEEK), polyvinylidene difluoride(PVDF), polysulfone, polyethylene, a thermal cure epoxy, an air dryepoxy, a phenolic epoxy, a phenolic polymer, polytetrafluoroethylene,fluorinated ethylene propylene, a ceramic-epoxy composite coating,ethylene chlorotrifluoroethylene, other polymers combinations thereof,or copolymers thereof. In some embodiments, the filter comprises a meshcomprising polyetheretherketone. In some embodiments, the mesh has apore size of less than about 200 microns, less than about 100 microns,less than about 50 microns, less than about 25 microns, less than about10 microns, less than about 2 microns, greater than about 200 microns,or greater than about 400 microns. In some embodiments, a mesh is awoven polymer or a polymer fabric. In some embodiments, the filter is amesh with a weave that is plain weave, twill weave, plain dutch weave,twill dutch weave, or combinations thereof. In some embodiments, thefilter comprises a stainless steel mesh. In some embodiments, the filtercomprises a stainless steel mesh coated to improve acid resistance witha material such as nickel, a nickel alloy, an oxide, or anotheracid-resistant material. In some embodiments, the filter comprisespolyamide, aromatic polyamide, polyvinylamine, polypyrrolidine,polyfuran, polyethersulfone, polysulfone, polypiperzine-amide,polybenzimidazoline, polyoxadiazole, acetylated cellulose, cellulose, apolymer with alternative functionalization of sulfonation,carboxylation, phosphorylation, or combinations thereof, other polymericlayer, or combinations thereof. In some embodiments, the filter furthercomprises a fabric, polymeric, composite, or metal support. In someembodiments, the filter comprises a metal material coated with oxide,epoxy, polymeric material, or combinations thereof that imbue chemicalresistance.

In some embodiments of the filter, the filters are weaved ofmonofilament or multifilament strands of material. In some embodimentsthe weave of the filter fabric is plain square, plain twilled, plaindutch, twilled dutch, reverse dutch, duplex dutch, betamesh dutch,basket weaved, or combinations thereof.

In some embodiments of the ion exchange reactor, the filter is locatedinside the tank, outside the tank (external to the tank), or is mountedin one or more ports through the wall of the tank. In some embodiments,the filter is a planar filter, a tubular filter, a hollow fiber tubefilter, a cartridge filter, Scheibler filter, Vallex filter, Sweetlandfilter, horizontal leaf filter, centrifugal discharge filter,compression filter, Nutsche filter, or a candle filter. In someembodiments, the ion exchange reactor may have more than about one, morethan about 5, more than about 20, or more than about 100 filters. Insome embodiments, a rotary fan press is used to separate liquid solutionfrom a slurry comprising a liquid solution and ion exchange particles.

In some embodiments, the filters are in the tank. In some embodiments,the filters are mounted in the tank at different heights. In someembodiments, the filters are mounted in a port or flange in the tankwall. In some embodiments, one or more filters is mounted at the bottomof one or more tanks. In some embodiments, one or more filters ismounted at the bottom of one or more columns that are mounted at thebottom of one or more tanks. In some embodiments, the filters areapproximately flush with the tank wall. In some embodiments withmultiple filters, the filters near the top of the tank are used whileion exchange particles are allowed to settle to the bottom of the tankunder the force of gravity. In some embodiments, the filters near thebottom of the tank are used after the ion exchange particles havesubstantially settled. In some embodiments, filters are arrangedvertically or horizontally. In some embodiments, filters form an arrayinside the volume or along the sides of the tank. In some embodiments,multiple filters are used in series or parallel. In some embodiments,multiple filters are used in series with varying pore size. In someembodiments, a filter comprises a smaller mesh mounted on a larger meshwhere the smaller mesh blocks ion exchange particles and the larger meshprovides strength to support the smaller mesh.

In some embodiments, liquid resources, acid solutions, or washingsolutions are removed from the tank through the filters. In someembodiments, the acid solutions are removed from the tank throughfilters near the bottom of the tank. In some embodiments, liquidresources are removed from the tank through filters near the top,middle, and bottom of the tank. In some embodiments, washing solutionsare removed from the tank through filters near the top, middle, andbottom of the tank.

In some embodiments, broken filters, or filters that no longer operatewithin acceptable range of their original specifications, are replacedduring operation of the ion exchange reactor or upon pausing operationof the ion exchange reactor. In some embodiments, multiple candlefilters are inserted into the tank and when a filter fails, pumpingthrough the filter is suspended while pumping through the other filtersis maintained. In some embodiments, a presence of ion exchange particlesin a tube or pipe connected to a filter is used to detect failure of thefilter. In some embodiments, one or more pressure sensors are used todetect failure of a filter, particle trap, solid-liquid separationapparatus, or combinations thereof.

In some embodiments, the ion exchange material is contained in acompartment with filters that allow permeation of liquid solutions intothe compartment. In some embodiments, the ion exchange material iscontained in a rotating compartment. In some embodiments, thecompartment may have baffled or other fixtures designed to guide liquidsolutions through the compartment. In some embodiments, the reactor is arotating bed reactor.

In some embodiments, the filter is a belt filter, plate-and-frame filterpress, pressure vessel containing filter elements, rotary drum filter,rotary disc filter, cartridge filter, a centrifugal filter with a fixedor moving bed, a metal screen, a perforate basket centrifuge, athree-point centrifuge, a peeler type centrifuge, or a pushercentrifuge. In some embodiments, the filter may use a scroll or avibrating device. In some embodiments, the filter is horizontal,vertical, or may use a siphon.

In some embodiments, a filter cake is prevented, limited, or removed byusing gravity, centrifugal force, an electric field, vibration, brushes,liquid jets, scrapers, intermittent reverse flow, vibration, crow-flowfiltration, or pumping suspensions across the surface of the filter. Insome embodiments, the slurry of ion exchange particles and liquid ismoved tangentially to the filter to limit cake growth. In someembodiments, gravitational, magnetic, centrifugal sedimentation, orother means of solid-liquid separation are used before, during, or afterfiltering to prevent cake formation.

In some embodiments, a filter comprises a screen, a metal screen, asieve, a sieve bend, a bent sieve, a high frequency electromagneticscreen, a resonance screen, or combinations thereof.

In some embodiments, a deep bed filter is used to remove ion exchangeparticles from a liquid resource stream before it is reinjected into theground.

Other Particle Traps

In some embodiments, one or more particle traps are a solid-liquidseparation apparatus.

In some embodiments of the ion exchange reactor, one or more particletraps are external particle traps located externally to the tank. Insome embodiments, a dilute slurry is removed from the tank, transferredto an external particle trap, and separated into a concentrated slurryand a solution with low or no suspended solids. In some embodiments, theconcentrated slurry is returned to the tank or transferred to adifferent tank. In some embodiments, ion exchange particles aretransferred from a brine tank to another brine tank, from an acid tankto another acid tank, from a washing tank to another washing tank, froma brine tank to a washing tank, from a washing tank to an acid tank,from an acid tank to a washing tank, or from an acid tank to a brinetank.

In some embodiments, the particle traps may use gravitationalsedimentation. In some embodiments, the particle traps may include asettling tank, a thickener, a clarifier, a gravity thickener. In someembodiments, the particle traps are operated in batch mode, semi-batchmode, semi-continuous mode, or continuous mode. In some embodiments, theparticle traps include a circular basin thickener with slurry enteringthrough a central inlet such that the slurry is dispersed into thethickener with one or more raking components that rotate and concentratethe ion exchange particles into a zone where the particles can leavethrough the bottom of the thickener.

In some embodiments, the particle traps include a deep cone, a deep conetank, a deep cone compression tank, or a tank wherein the slurry iscompacted by weight. In some embodiments, the particle traps include atray thickener with a series of thickeners oriented vertically with acenter axle and raking components. In some embodiments, the particletraps include a lamella type thickener with inclined plates or tubesthat may be smooth, flat, rough, or corrugated. In some embodiments, theparticle traps include a gravity clarifier that may be a rectangularbasin with feed at one end and overflow at the opposite end optionallywith paddles and/or a chain mechanism to move particles.

In some embodiments, the particle traps use centrifugal sedimentation.In some embodiments, the particle traps may include a tubularcentrifuge, a multi-chamber centrifuge, a conical basket centrifuge, ascroll-type centrifuge, a sedimenting centrifuge, or a disc centrifuge.In some embodiments, particles are discharged continuously orintermittently from the centrifuge. In some embodiments, the particletrap is a hydrocyclone. In some embodiments, the particle trap is anarray of hydrocyclones or centrifuges in series and/or in parallel. Insome embodiments, sumps are used to reslurry the ion exchange particles.In some embodiments, the hydrocyclones may have multiple feed points. Insome embodiments, a hydrocyclone is used upside down. In someembodiments, liquid is injected near the apex of the cone of ahydrocyclone to improve sharpness of cut. In some embodiments, a weirrotates in the center of the particle trap with a feed of slurried ionexchange particles entering near the middle of the particle trap, andion exchange particles get trapped at the bottom and center of theparticle trap due to a “teacup effect”.

In some embodiments, the particle trap may use magnetic separation. Insome embodiments, the ion exchange particles are magnetic. In someembodiments, acid resistant magnetic particles such as SiO₂-coatedmagnetite or other coated or uncoated magnetic materials are attached tothe surface of the ion exchange particles to enable magnetic separation.

In some embodiments, the particle trap is a collection of particle trapswith similar or different mechanisms. In some embodiments, particletraps based on gravity, magnetism, centrifugal forces, or combinationsthereof are located inside or outside the tank of the ion exchangereactor.

In some embodiments, the ion exchange particles are washed usingcounter-current flows of the ion exchange particles and a washingliquid. In some embodiments, the ion exchange particles are treated withbrine or acid liquids using counter-current flows of the ion exchangeparticles and the liquids. In some embodiments, the counter-currentwashing of solids is performed using a series of particle traps orseparators. In some embodiments, and additional particle trap orseparator is located at the end of the liquid flow of thecounter-current circuit to limit loss of particles. In some embodiments,counter-current washing is used to minimize use of fresh water.

Staged Flows

An aspect of the invention described herein is a staged ion exchangereactor for extracting lithium from liquid resources, comprising: a) atank containing ion exchange particles with associated particle traps;b) one or more tanks containing brine at various stages of delithiation;and c) one or more tanks containing acid at various stages oflithiation.

An aspect of the invention described herein is a staged ion exchangereactor for extracting lithium from liquid resources, comprising: a) atank containing ion exchange particles with associated particle traps;and b) one or more tanks containing brine at various stages ofdelithiation.

An aspect of the invention described herein is a staged ion exchangereactor for extracting lithium from liquid resources, comprising: a) atank containing ion exchange particles with associated particle traps;and b) one or more tanks containing acid at various stages oflithiation.

In some embodiments, the staged ion exchange reactor contacts ionexchange particles that are saturated with hydrogen in contact withbrine that is partially delithiated to maximize lithium recovery fromthe brine. In some embodiments, the staged ion exchange reactor contactsion exchange particles that are saturated with lithium in contact withacid that is partially lithiated to maximize conversion of protons inthe acid to lithium ions.

In some embodiments, the staged ion exchange reactor contacts ionexchange particles that are nearly saturated with lithium in contactwith fresh brine to fully saturated the ion exchange particles withlithium and maximize lithium uptake by the particles. In someembodiments, the staged ion exchange reactor contacts ion exchangeparticles that are nearly saturated with protons in contact with freshacid to fully saturated the ion exchange particles with protons andmaximize lithium elution from the particles.

Interchange Network

In some embodiments, a plurality of ion exchange reactors are joined toform an interchange network comprising brine circuits, washing circuits,or acid circuits. In some embodiments of the brine circuit, brine flowsthrough a first reactor in the brine circuit, then into a next reactorin the brine circuit, and so on, such that lithium is removed from thebrine as the brine flows through one or more reactors. In someembodiments of the acid circuit, acid flows through a first reactor inthe acid circuit, then into the next reactor in the acid circuit, and soon, such that lithium is eluted from the columns with acid to produce alithium eluate. In some embodiments of the water washing circuit, waterflows through a first reactor in the water washing circuit, thenoptionally into a next reactor in the water washing circuit, and so on,such that residual brine or other impurities are washed out. In someembodiments, particle traps are used to retain ion exchange particleswithin individual reactors in a circuit. In some embodiments, particletraps are used to move ion exchange particles in a counter-currentdirection through a series of reactors within the brine, washing, and/oracid circuits, or to move ion exchange particles between the differentcircuits.

In some embodiments of the interchange network, ion exchange reactorsare interchanged between the brine circuit, the water washing circuit,and the acid circuit. In some embodiments, the first reactor in thebrine circuit is loaded with lithium and then interchanged into thewater washing circuit to remove residual brine. In some embodiments, thefirst reactor in the water washing circuit is washed to remove residualbrine, and then interchanged to the acid circuit, where lithium iseluted with acid to form a lithium eluate. In some embodiments, thefirst reactor in the acid circuit is eluted with acid and theninterchanged into the brine circuit to absorb lithium from the brine. Insome embodiments, two water washing circuits are used to wash thereactors after both the brine circuit and the acid circuit. In someembodiments of the reactor interchange system, only one water washingcircuit is used to wash the columns after the brine circuit, whereasexcess acid is neutralized with base or washed out of the reactors inthe brine circuit.

In some embodiments of the interchange network, the first reactor in thebrine circuit is interchanged to become the last reactor in the waterwashing circuit. In some embodiments, the first reactor in the waterwashing circuit is interchanged to become the last reactor in the acidcircuit. In some embodiments, the first reactor in the acid circuit isinterchanged to become the last reactor in the brine circuit or the lastreactor in a water washing circuit for acid removal.

Other Aspects

In some embodiments, flows of brine through the reactor are operated inbatch, semi-batch, semi-continuous, or continuous modes of operation. Insome embodiments, flows of washing solution through the reactor areoperated in batch, semi-continuous, or continuous modes of operation. Insome embodiments, flows of acid solution through the reactor areoperated in batch, semi-continuous, or continuous modes of operation. Insome embodiments, ion exchange particles are moved between a pluralityof reactors. In some embodiments, ion exchange particles are movedbetween a plurality of reactors in an opposite direction to the flows ofbrine, washing solution, and acid.

In some embodiments, air pumps, water pumps, or vacuum pumps are used tomove water, brine, acid, slurries, or other solutions. In someembodiments, a vacuum system is used to move water, brine, acid,slurries, or other solutions. In some embodiments, one or more tanks,columns, or other vessels are pressurized to move water, brine, acid,slurries, or other solutions. In some embodiments, one or more tanks,columns, or other vessels are pressurized to move water, brine, acid, orother solutions through a filter, particle trap, or other solid-liquidseparation apparatus. In some embodiments, a vacuum is applied tofilters in contact with the ion exchange material/fluid suspension tosuck fluid out of the reactor while leaving the ion exchange materialinside the reactor. In some embodiments, a vacuum valve is installedapproximately 6 inches from the filter inside the line which is closedwhen the filter is to be backwashed. In some embodiments, a vacuum valveis installed approximately 4 inches from the filter inside the linewhich is closed when the filter is to be backwashed. In someembodiments, a vacuum valve is installed approximately 8 inches from thefilter inside the line which is closed when the filter is to bebackwashed. In some embodiments, for backwashing, pressurized air ispumped through the filter to break up the cake on the other side of thefilter. In some embodiments, to resume filtering of the fluid from thesuspension, the vacuum valve is opened again to re-expose the filter tovacuum. In some embodiments, a series of vacuum valves are used tominimize loss of vacuum from the vacuum/drainage lines.

In some embodiments, a washing solution is used to remove residualbrine, residual acid, or other impurities from the ion exchangeparticles. In some embodiments, the washing solution is water, waterwith pH adjusted, an aqueous solution, or a non-aqueous solution. Insome embodiments, ion exchange particles are removed from the tank andloaded into a column where they are washed. In some embodiments, ionexchange particles are removed from the tank and loaded into a columnwhere they are washed to remove residual brine. In some embodiments, ionexchange particles are removed from the tank and loaded into a columnwhere they are washed to remove residual acid. In some embodiments, theion exchange particle form a packed bed, a settled bed, a fluidized bed,or combinations thereof. In some embodiments, the ion exchange particlesare moved between a tank and a column. In some embodiments, the ionexchange particles are moved between a tank where they are fluidized anda column where they form a packed or settled bed. In some embodiments,one or more columns are directly attached to one or more tanks. In someembodiments, one or more columns are mounted at the bottom of one ormore tanks so the ion exchange particles can settle from the tank intothe column. In some embodiments, one or more columns are mounted at thebottom of one or more cone-bottom tanks so the ion exchange particlescan settle from the tank into the column. In some embodiments, one ormore columns are mounted at the bottom of one or more tanks so the ionexchange particles can settle from the tank into the column under theforce of gravity and or with the flow of solution.

In some embodiments, a washing solution containing EDTA, disodium EDTA,or other anti-scalants is used to remove CaSO₄, MgSO₄, SrSO₄, BaSO₄,MgCO₃, CaCO₃, BaCO₃, SrCO₃, sulfate scale, carbonate scale, or otherscale from the ion exchange reactor. In some embodiments, ananti-scalants wash is performed before or after each brine, water, oracid treatment. In some embodiments, an anti-scalants wash is performedafter a number of ion exchange cycles that is less than about 10, lessthan about 50, or less than about 200.

In some embodiments, ion exchange particles are replaced from thereactor after the performance of these ion exchange particles hasdegraded in terms of lithium uptake capacity, lithium selectivity,lithium uptake kinetics, chemical stability, or mechanical stability. Insome embodiments, ion exchange particles are replaced in one or more ionexchange reactors in a network of ion exchange reactors with minimaldisruption to operations.

In some embodiments, base is added to the ion exchange reactor before,during, or after lithium uptake from a liquid resource. In someembodiments base is added as a solution, as an aqueous solution, as acomponent of a slurry, or as a solid. Base serves to neutralize protonsrelease by the ion exchange material and maintain the pH of the liquidresource in a range of about 5-7, about 3-8, or about 1-9.

In some embodiments, the ion exchange reactor has a plunger, piston, orother mechanical device that compacts the ion exchange particles onto afilter while forcing liquid solution through the filter. In someembodiments, the ion exchange reactor is pressurized to force fluidthrough the filter at a higher rate. In some embodiments, a vacuum isused on the effluent side of the filter to promote higher filtrationrates.

In some embodiments, flows of liquid resource, washing solution, or acidsolution are recirculated through an ion exchange reactor. In someembodiments, recirculation of brine from the bottom of the reactorserves to create a fluidized bed, or partially fluidized bed, of ionexchange particles. In some embodiments, flows of acid, brine, water, orother solutions are injected at the bottom of the tank to fluidize orsuspend ion exchange particles from the bottom of the tank. In someembodiments, flows of acid, brine, water, or other solutions areinjected at the bottom of the tank and removed at the top of the tank.In some embodiments, flows of acid, brine, water, or other solutions aremoved as part of a network of reactors and are injected at the bottom ofthe tank to fluidize or suspend ion exchange particles from the bottomof the tank. In some embodiments, flows of acid, brine, water, or othersolutions are moved as part of a network of continuously-operated orsemi-continuously-operated reactors and are injected at the bottom ofthe tank to fluidize or suspend ion exchange particles from the bottomof the tank.

In some embodiments, the ion exchange reactor is equipped with aspraying system to wash ion exchange particles off the internal surfacesof the tank and move the ion exchange particles to the bottom of thetank.

In some embodiments, lithium is eluted from the ion exchange particlesusing acid that is added all at once, titrated in various aliquots ofsimilar or different concentrations. In some embodiments, lithiumelution from the ion exchange particles are monitored or controlledusing pH measurement and acid titration. In some embodiments, acid isadded to a slurry comprising water and ion exchange particles, and theacid concentration added to the slurry is higher than the final acidconcentration of the slurry after the acid is added.

In some embodiments, pH changes in the brine, acid, or water solutionsare monitored to determine timing of lithium uptake, lithium elution, orwashing processes.

In some embodiments, ion exchange particles are added or removed at thetop or bottom of a tank or column in the ion exchange reactor. In someembodiments, brine, water, or acid solutions are added or removed at thetop or bottom of a tank or column in the ion exchange reactor. In someembodiments, ion exchange particles are added to the top of a tank orcolumn in the ion exchange reactor and may settled to the bottom. Insome embodiments, ion exchange particles are added to the top of a tankor column in the ion exchange reactor and may settled to the bottom asbrine moves upwards through the tank or column. In some embodiments, ionexchange particles are added to the top of a tank or column in the ionexchange reactor and may settle to the bottom at a rate that iscontrolled by the upward flow of brine, water, or acid solutions thatare added at the bottom of the column and removed from the top of thecolumn.

In some embodiments, the tank is comprised of a material that is apolymer, a metal, a ceramic, an alloy, stainless steel, a plastic-linedalloy, an oxide-lined alloy, fiberglass, composite materials, orcombinations thereof. In some embodiments, the tank is comprised ofPVDF, PE, PP, PVC, PTFE, other acid-resistant materials, or combinationsthereof.

In some embodiments, the pH of the brine resource decreases when thebrine resource is contacted with ion exchange particles due to lithiumuptake and proton release by the ion exchange particles. In someembodiments, base is added to the liquid resource to control the pH inthe range of about 5-7, about 4-8, or about 1-9. In some embodiments,the base is added as a solid, as a slurry, as a liquid solution, or asan aqueous solution. In some embodiments, the base may comprise CaO,Ca(OH)₂, Mg(OH)₂, NaOH, KOH, Sr(OH)₂, Ba(OH)₂, or combinations thereof.

In some embodiments of the ion exchange reactor or reactor system,flocculants are used to aid sedimentation or separation.

Ion Exchange Particles

In some embodiments, ion exchange particles are coated or uncoated ionexchange particles. In some embodiments, the ion exchange particlescomprise an ion exchange material selected from the following list:LiFePO₄, LiMnPO₄, Li₂MO₃ (M=Ti, Mn, Sn), Li₄Ti₅O₁₂, Li₄Mn₅O₁₂, LiMn₂O₄,Li₁₆Mn₁₆O₄, LiMO₂ (M=Al, Cu, Ti), Li₄TiO₄, Li₇Ti₁₁O₂₄, Li₃VO₄, Li₂Si₃O₇,Li₂CuP₂O₇, Al(OH)₃, LiCl.xAl(OH)₃.yH₂O, SnO₂.xSb₂O₅.yH₂O,TiO₂.xSb₂O₅.yH₂O, solid solutions thereof, and combinations thereof. Insome embodiments, an ion exchange material comprises LiFePO₄, Li₂SnO₃,Li₂MnO₃, Li₂TiO₃, Li₄Ti₅O₁₂, Li₄Mn₅O₁₂, Li₁₆Mn₁₆O₄, solid solutionsthereof, or combinations thereof.

In some embodiments, the ion exchange particles have a coating thatcomprises Nb₂O₅, Ta₂O₅, MoO₂, TiO₂, ZrO₂, SnO₂, SiO₂, Li₂O, Li₂TiO₃,Li₂ZrO₃, Li₂MoO₃, LiNbO₃, LiTaO₃, Li₂SiO₃, Li₂Si₂O₅, Li₂MnO₃, ZrSiO₄,AlPO₄, LaPO₄, ZrP₂O₇, MoP₂O₇, Mo₂P₃O₁₂, BaSO₄, AlF₃, SiC, TiC, ZrC,Si₃N₄, ZrN, BN, carbon, graphitic carbon, amorphous carbon, hard carbon,diamond-like carbon, solid solutions thereof, or combinations thereof.In some embodiments, a coating material comprises TiO₂, ZrO₂, SiO₂,Li₂TiO₃, Li₂ZrO₃, Li₂MnO₃, ZrSiO₄, LiNbO₃, or combinations thereof.

In some embodiments, the ion exchange particles are porous, non-porous,or composites. In some embodiments, the ion exchange particles arecomprised of coated or uncoated ion exchange material embedded in amatrix. In some embodiments, the matrix is PVDF, polystyrene, other acidresistant polymer, ceramic binder, silica binder, or combinationsthereof.

In a further aspect, a coating material comprises a chloro-polymer, afluoro-polymer, a chloro-fluoro-polymer, a hydrophilic polymer, ahydrophobic polymer, co-polymers thereof, mixtures thereof, orcombinations thereof. In a further aspect, a coating material comprisesa co-polymer, a block co-polymer, a linear polymer, a branched polymer,a cross-linked polymer, a heat-treated polymer, a solution processedpolymer, co-polymers thereof, mixtures thereof, or combinations thereof.In a further aspect, a coating material comprises polyethylene, lowdensity polyethylene, high density polyethylene, polypropylene,polyester, polytetrafluoroethylene (PTFE), types of polyamide, polyetherether ketone (PEEK), polysulfone, polyvinylidene fluoride (PVDF), poly(4-vinyl pyridine-co-styrene) (PVPCS), polystyrene (PS), polybutadiene,acrylonitrile butadiene styrene (ABS), polyvinyl chloride (PVC),ethylene tetrafluoroethylene polymer (ETFE),poly(chlorotrifluoroethylene) (PCTFE), ethylene chlorotrifluoro ethylene(Halar), polyvinylfluoride (PVF), fluorinated ethylene-propylene (FEP),perfluorinated elastomer, chlorotrifluoroethylenevinylidene fluoride(FKM), perfluoropolyether (PFPE), perfluorosulfonic acid (Nafion),polyethylene oxide, polyethylene glycol, sodium polyacrylate,polyethylene-block-poly(ethylene glycol), polyacrylonitrile (PAN),polychloroprene (neoprene), polyvinyl butyral (PVB), expandedpolystyrene (EPS), polydivinylbenzene, co-polymers thereof, mixturesthereof, or combinations thereof. In a further aspect, a coatingmaterial comprises polyvinylidene fluoride (PVDF), polyvinyl chloride(PVC), ethylene chlorotrifluoro ethylene (Halar), poly (4-vinylpyridine-co-styrene) (PVPCS), polystyrene (PS), acrylonitrile butadienestyrene (ABS), expanded polystyrene (EPS), polyphenylene sulfide,sulfonated polymer, carboxylated polymer, other polymers, co-polymersthereof, mixtures thereof, or combinations thereof.

In some embodiments, the coated particle comprises an ion exchangematerial selected from the group consisting of LiFePO₄, Li₂SnO₃,Li₂MnO₃, Li₂TiO₃, Li₄Ti₅O₁₂, Li₄Mn₅O₁₂, Li₁₆Mn₁₆O₄, solid solutionsthereof, or combinations thereof, and a coating material comprisingTiO₂, ZrO₂, SiO₂, Li₂TiO₃, Li₂ZrO₃, Li₂MnO₃, ZrSiO₄, LiNbO₃,polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), ethylenechlorotrifluoro ethylene (Halar), poly (4-vinyl pyridine-co-styrene)(PVPCS), polystyrene (PS), acrylonitrile butadiene styrene (ABS),expanded polystyrene (EPS), polyphenylene sulfide, sulfonated polymer,carboxylated polymer, other polymers, co-polymers thereof, mixturesthereof, or combinations thereof.

In a further aspect, a coating is deposited onto an ion exchangeparticle by dry mixing, mixing in solvent, emulsion, extrusion, bubblingone solvent into another, casting, heating, evaporating, vacuumevaporation, spray drying, vapor deposition, chemical vapor deposition,microwaving, hydrothermal synthesis, polymerization, co-polymerization,cross-linking, irradiation, catalysis, foaming, other depositionmethods, or combinations thereof. In a further aspect, a coating isdeposited using a solvent comprising n-methyl-2-pyrrolidone, dimethylsulfoxide, tetrahydrofuran, dimethylformamide, dimethylacetamide, methylethyl ketone, ethanol, acetone, other solvents, or combinations thereof.

Liquid Resource

In some embodiments, the liquid resource is selected from the followinglist: a natural brine, a dissolved salt flat, a geothermal brine,seawater, concentrated seawater, desalination effluent, a concentratedbrine, a processed brine, liquid from an ion exchange process, liquidfrom a solvent extraction process, a synthetic brine, leachate fromores, leachate from minerals, leachate from clays, leachate fromrecycled products, leachate from recycled materials, or combinationsthereof. In some embodiments, a liquid resource is selected from thefollowing list: a natural brine, a dissolved salt flat, a concentratedbrine, a processed brine, a synthetic brine, a geothermal brine, liquidfrom an ion exchange process, liquid from a solvent extraction process,leachate from minerals, leachate from clays, leachate from recycledproducts, leachate from recycled materials, or combinations thereof. Insome embodiments, the liquid resource is optionally pre-treated prior toentering the ion exchange reactor to remove suspended solids,hydrocarbons, organic molecules, or other chemical or ionic species. Insome embodiments, the liquid resource is optionally fed into the ionexchange reactor without any pre-treatment following from its source. Insome embodiments, the liquid resource is injected into a reservoir, saltlake, salt flat, basin, or other geologic deposit after lithium has beenremoved from the liquid resource. In some embodiments, other species arerecovered from the liquid resource before or after lithium recovery. Insome embodiments, the pH of the liquid resource is adjusted before,during, or after lithium recovery.

Eluate Processing

In some embodiments, the lithium eluate solution that is yielded fromthe ion exchange reactor is further processed into lithium chemicalsselected from the following list: lithium sulfate, lithium chloride,lithium carbonate, lithium phosphate, lithium hydroxide, lithium metal,lithium metal oxide, lithium metal phosphate, lithium sulfide, orcombinations thereof. In some embodiments, the lithium eluate solutionthat is yielded from the ion exchange reactor is further processed intolithium chemicals that are solid, aqueous, liquid, slurry form,hydrated, or anhydrous.

In some embodiments, the lithium eluate solution that is yielded fromthe ion exchange reactor is further processed using acid recovery, acidrecycling, acid regeneration, distillation, reverse osmosis,evaporation, purification, chemical precipitation, membraneelectrolysis, or combinations thereof.

Methods

An aspect of the invention described herein is a method of generating alithium eluate solution from a liquid resource, comprising: providing anion exchange reactor comprising a tank, ion exchange particles thatselectively absorb lithium from a liquid resource and elute a lithiumeluate solution when treated with an acid solution after absorbinglithium ions from said liquid resource, one or more particle traps, andprovision to modulate pH of said liquid resource; flowing a liquidresource into said ion exchange reactor thereby allowing said ionexchange particles to selectively absorb lithium from said liquidresource; treating said ion exchange particles with an acid solution toyield said lithium eluate solution; and passing said lithium eluatesolution through said one or more particle traps to collect said lithiumeluate solution.

An aspect of the invention described herein is a method of generating alithium eluate solution from a liquid resource, comprising: providing anion exchange reactor comprising (i) a tank with a conical shape, whereinsaid conical shape allows said ion exchange particles to settle into asettled bed so that liquid can be removed from above said settled bed;(ii) ion exchange particles that selectively absorb lithium from saidliquid resource and elute said lithium eluate solution when treated withan acid solution after absorbing lithium from said liquid resource;(iii) one or more particle traps located at the bottom of said tank,wherein said one or more particle traps comprise one or more meshes; and(iv) provision to modulate pH of said liquid resource, wherein saidmodulation of said pH of said liquid resource is configured to occur inthe tank or prior to injection of said liquid resource into the tank;flowing a liquid resource into said ion exchange reactor therebyallowing said ion exchange particles to selectively absorb lithium fromsaid liquid resource; treating said ion exchange particles with an acidsolution to yield said lithium eluate solution; and passing said lithiumeluate solution through said one or more particle traps to collect saidlithium eluate solution.

An aspect of the invention described herein is a method of generating alithium eluate solution from a liquid resource, comprising: providing anion exchange reactor comprising: (i) a tank with a conical shape,wherein said conical shape allows said ion exchange particles to settleinto a settled bed so that liquid can be removed from above said settledbed; (ii) ion exchange particles that selectively absorb lithium fromsaid liquid resource and elute said lithium eluate solution when treatedwith an acid solution after absorbing lithium from said liquid resource;(iii) one or more particle traps located at the bottom of said tank,wherein said one or more particle traps comprise multi-layered meshes;and (iv) provision to modulate pH of said liquid resource, wherein saidmodulation of said pH of said liquid resource is configured to occur inthe tank or prior to injection of said liquid resource into the tank;flowing a liquid resource into said ion exchange reactor therebyallowing said ion exchange particles to selectively absorb lithium fromsaid liquid resource; treating said ion exchange particles with an acidsolution to yield said lithium eluate solution; and passing said lithiumeluate solution through said one or more particle traps to collect saidlithium eluate solution.

In some embodiments, the tank has a conical shape. In some embodiments,the tank has a partial conical shape. In some embodiments, the conicalshape allows the ion exchange particles to settle into a settled bed sothat liquid can be removed from above the settled bed. In someembodiments, the partial conical shape allows the ion exchange particlesto settle into a settled bed so that liquid can be removed from abovethe settled bed.

In some embodiments, modulation of the pH of the liquid resource occursin the tank. In some embodiment, modulation of the pH of the liquidresource occurs prior to injection into the tank. In some embodiments,one or more particle traps comprise one or more filters inside the tank.In some embodiments, one or more particle traps comprise one filter. Insome embodiments, one or more particle traps comprise one filter. Insome embodiments, one or more particle traps comprise two filters. Insome embodiments, one or more particle traps comprise three filters. Insome embodiments, one or more particle traps comprise four filters. Insome embodiments, one or more particle traps comprise five filters.

In some embodiments, one or more particle traps is located at the bottomof the tank. In some embodiments, one or more particle traps is locatedclose to the bottom of the tank. In some embodiments, one or moreparticle traps is located above the bottom of the tank.

In some embodiments, one or more particle traps comprise one or moremeshes. In some embodiments, one or more particle traps comprises onemesh. In some embodiments, one or more particle traps comprises twomeshes. In some embodiments, one or more particle traps comprises threemeshes. In some embodiments, one or more particle traps comprises fourmeshes. In some embodiments, one or more particle traps comprises fivemeshes. In some embodiments, all the meshes of the one or more particletraps are identical. In some embodiments, at least one of the meshes ofthe one or more particle traps is not identical to the rest of themeshes of the one or more particle traps.

In some embodiments, one or more meshes comprise a pore space of lessthan about 200 microns, less than about 175 microns, less than about 150microns, less than about 100 microns, less than about 75 microns, lessthan about 50 microns, less than about 25 microns, less than about 10microns, more than about 1 micron, more than about 5 micron, more thanabout 10 microns, more than about 20 microns, more than about 30microns, more than about 40 microns, more than about 50 microns, morethan about 60 microns, more than about 70 microns, more than about 80microns, more than about 90 microns, more than about 100 microns, morethan about 125 microns, more than about 150 microns, more than about 175microns from about 1 micron to about 200 microns, from about 5 micronsto about 175 microns, from about 10 microns to about 150 microns, fromabout 10 microns to about 100 microns, from about 10 microns to about 90microns, from about 10 microns to about 80 microns, from about 10microns to about 70 microns, from about 10 microns to about 60 microns,or from about 10 microns to about 50 microns.

In some embodiments, one or more particle traps comprise multi-layeredmeshes. In some embodiments, the multi-layered meshes comprise at leastone finer mesh for filtration and at least one coarser mesh forstructural support. In some embodiments, one or more particle trapscomprise one or more meshes supported by a structural support. In someembodiments, one or more particle traps comprise one or more polymermeshes. In some embodiments, the one or more polymer meshes are selectedfrom the group consisting of polyetheretherketone, ethylenetetrafluorethylene, polyethylene terephthalate, polypropylene, andcombinations thereof.

In some embodiments, one or more particle traps comprise one or moremeshes comprising a metal wire mesh. In some embodiments, the metal wiremesh is coated with a polymer. In some embodiments, the ion exchangereactor is configured to move said ion exchange particles into one ormore columns for washing. In some embodiments, the ion exchange reactoris configured to allow the ion exchange particles to settle into one ormore columns for washing. In some embodiments, the columns are affixedto the bottom of said tank. In some embodiments, the one or moreparticle traps comprise one or more filters mounted in one or more portsthrough the wall of said tank.

In some embodiments, the one or more particle traps comprise one or morefilters external to said tank, and with provision for fluidcommunication between said one or more filters and said tank. In someembodiments, the one or more particle traps comprise one or more gravitysedimentation devices external to said tank, and with provision forfluid communication between said one or more gravity sedimentationdevices and said tank.

In some embodiments, one or more particle traps comprise one or moregravity sedimentation devices internal to said tank. In someembodiments, one or more particle traps comprise one or more centrifugalsedimentation devices external to said tank, and with provision forfluid communication between said one or more centrifugal sedimentationdevices and said tank In some embodiments, one or more particle trapscomprise one or more centrifugal sedimentation devices internal to saidtank. In some embodiments, one or more particle traps comprise one ormore settling tanks, one or more centrifugal devices, or combinationsthereof external to said tank, and with provision for fluidcommunication between said one or more settling tanks, centrifugaldevices, or combinations thereof, and said tank. In some embodiments,one or more particle traps comprise one or more meshes, one or morecentrifugal devices, or combinations thereof external to said tank, andwith provision for fluid communication between said one or more meshes,centrifugal devices, or combinations thereof, and said tank. In someembodiments, one or more particle traps comprise one or more settlingtanks, one or more meshes, or combinations thereof external to saidtank, and with provision for fluid communication between said one ormore settling tanks, meshes, or combinations thereof, and said tank. Insome embodiments, one or more particle traps comprise one or moremeshes, one or more settling tanks, one or more centrifugal devices, orcombinations thereof external to said tank, and with provision for fluidcommunication between said one or more meshes, one or more settlingtanks, centrifugal devices, or combinations thereof, and said tank.

In some embodiments, the ion exchange particles are stirred. In someembodiments, the ion exchange particles are stirred by a mixer. In someembodiments, the ion exchange particles are stirred by a propeller. Insome embodiments, the ion exchange particles are fluidized by pumpingsolution into the tank near the bottom of the tank. In some embodiments,the ion exchange particles are fluidized by pumping solution from thetank back into the tank near the bottom of the tank. In someembodiments, the ion exchange particles are fluidized by pumping aslurry of the ion exchange particles from near the bottom of the tank toa higher level in the tank.

In some embodiments, the method further comprises one or more stagedelution tanks, wherein intermediate eluate solutions comprising mixturesof protons and lithium ions are stored and used further to elute lithiumfrom said ion exchange particles that are freshly lithiated. In someembodiments, the method further comprises one or more staged elutiontanks, wherein intermediate eluate solutions comprising mixtures ofprotons and lithium ions are mixed with additional acid and used furtherto elute lithium from said ion exchange particles.

In some embodiments, the ion exchange particles further comprise acoating material. In some embodiments, the coating material is apolymer. In some embodiments, the coating of the coating materialcomprises a chloro-polymer, a fluoro-polymer, a chloro-fluoro-polymer, ahydrophilic polymer, a hydrophobic polymer, co-polymers thereof,mixtures thereof, or combinations thereof.

EXAMPLES Example 1: Ion Exchange Reactor with Conical Bottom and MountedFilters

Lithium is extracted from a brine using coated ion exchange particles.The brine is an aqueous solution containing 50,000 mg/L Na, 20,000 mg/LCa, 3,000 mg/L Mg, and 500 ppm Li. The coated ion exchange particles arecomprised of an ion exchange material and a coating material. The ionexchange material is Li₄Mn₅O₁₂ and the coating material is ZrO₂. Theparticles are comprised of 96 wt. % active material and 4 wt. % ofcoating material. The particles have a mean diameter of 30 microns, andthe coating thickness is approximately 100 nm. The particles are createdby first synthesizing Li₄Mn₅O₁₂ via a solid state method and then thecoating is deposited on the surface of the Li₄Mn₅O₁₂ using Zr(IV)propoxide as a precursor.

The ion exchange particles are loaded into an ion exchange reactor shownin FIG. 1. The ion exchange reactor comprises a conical tank (101), aPEEK 12 um mesh mounted on a flange at an opening in the tank wall sothat the mesh is approximately flush with the tank wall (102) fitted toa PVC tube to allow fluid to flow into and out of the tank through themesh while the ion exchange particles and retained inside the tank, anoverhead stirrer (103), a pH controller (104), and a spraying system(not shown) at the top of the tank with one or more nozzles positionedto spray water to wash ion exchange particles off the sides of the tankand down to the bottom of the tank.

The particles are loaded into the tank in an aqueous slurry. 1.5N H₂SO₄acid is pumped into the tank through the PEEK mesh to create a slurrywith H₂SO₄ at a normality of 0.75N. The acid is stirred with the ionexchange particle to yield Li₂SO₄ in solution. During acid treatment,the particles absorb hydrogen while releasing lithium. The Li₄Mn₅O₁₂active material is converted to a protonated state with ahydrogen-enriched composition. The ZrO₂ coating allows diffusion ofhydrogen and lithium respectively to and from the active material whileproviding a protective barrier that limits dissolution of manganese andoxygen from the active material. After 40 minutes, the eluate solutionis collected from the tank through the PEEK mesh for elemental analysisto measure the eluate composition.

After treatment in acid, the protonated particles are treated with brinewherein the particles absorb lithium while releasing hydrogen. The brineis pumped into the tank through the PEEK mesh. The particles areconverted from a protonated state to a lithiated state with alithium-enriched composition. An aqueous solution of NaOH is added tothe tank to maintain the pH of the brine at 6. After 4 hours, the spentbrine is removed from the tank through the PEEK mesh. The ion exchangeparticles are then washed with water through the spraying system. Theparticles are washed three times with water, and the water is drainedfrom the tank through the PEEK mesh, leaving an aqueous slurry of theion exchange particles at the bottom of the tank.

The lithiated material is then treated again with acid to yield lithiumin solution as described previously. The cycle of protonation andlithiation is repeated to extract lithium from the brine and yield aLi₂SO₄ solution. Dissolution and degradation of the active material inacid is limited due to the coating providing a protective barrier.Dissolution of the active material is measured by through elementalanalysis of the acid solution following stirring. After 25 ion exchangecycles, there is no measurable loss of lithium uptake capacity in theion exchange material and lithium recovery from the brine solution isapproximately 65% for each cycle.

Example 2: Ion Exchange Reactor with Conical Bottom and Internal Filters

Lithium is extracted from a brine using coated ion exchange particles.The brine is an aqueous solution containing 50,000 mg/L Na, 20,000 mg/LCa, 3,000 mg/L Mg, and 500 ppm Li. The coated ion exchange particles arecomprised of an ion exchange material and a coating material. The ionexchange material is Li₄Mn₅O₁₂ and the coating material is SiO₂. Theparticles are comprised of 94 wt. % active material and 6 wt. % ofcoating material. The particles have a mean diameter of 30 microns, andthe coating thickness is approximately 400 nm. The particles are createdby first synthesizing Li₄Mn₅O₁₂ via a solid state method and then thecoating is deposited on the surface of the Li₄Mn₅O₁₂ using tetraethylorthosilicate (TEOS) as a precursor.

The ion exchange particles are loaded into an ion exchange reactor shownin FIG. 2. The ion exchange reactor comprises a conical tank (201), twointernal candle filters comprising a PEEK 12 um mesh (202) fitted to aPVC pipe to allow fluid to flow into and out of the tank through themesh while the ion exchange particles are retained inside the tank, anoverhead stirrer (203), a pH controller (204), and a spraying system(not shown) at the top of the tank with one or more nozzles positionedto spray water to wash ion exchange particles off the sides of the tankand down to the bottom of the tank.

The particles are loaded into the tank in an aqueous slurry. 1.5N HClacid is pumped into the tank through the PEEK mesh to create a slurrywith HCl at a normality of 0.75N. The acid is stirred with the ionexchange particle to yield LiCl in solution. During acid treatment, theparticles absorb hydrogen while releasing lithium. The Li₄Mn₅O₁₂ activematerial is converted to a protonated state with a hydrogen-enrichedcomposition. The SiO₂ coating allows diffusion of hydrogen and lithiumrespectively to and from the active material while providing aprotective barrier that limits dissolution of manganese and oxygen fromthe active material. After 40 minutes, the eluate solution is collectedfrom the tank through the PEEK mesh for elemental analysis to measurethe eluate composition.

After treatment in acid, the protonated particles are treated with brinewherein the particles absorb lithium while releasing hydrogen. The brineis pumped into the tank through an opening in the top of the tank. Theparticles are converted from a protonated state to a lithiated statewith a lithium-enriched composition. An aqueous solution of NaOH isadded to the tank to maintain the pH of the brine at 7. After 6 hours,the spent brine is removed from the tank through the PEEK mesh. The ionexchange particles are then washed with water through the sprayingsystem. The particles are washed three times with water, and the wateris drained from the tank through the PEEK mesh, leaving an aqueousslurry of the ion exchange particles at the bottom of the tank.

The lithiated material is then treated again with acid to yield lithiumin solution as described previously. The cycle of protonation andlithiation is repeated to extract lithium from the brine and yield aLiCl solution. Dissolution and degradation of the active material inacid is limited due to the coating providing a protective barrier.

Example 3: Ion Exchange Reactor with Conical Bottom and External Filter

Lithium is extracted from a brine using coated ion exchange particles.The brine is an aqueous solution containing 70,000 mg/L Na, 1,000 mg/LCa, 5,000 mg/L Mg, and 200 ppm Li. The coated ion exchange particles arecomprised of an ion exchange material and a coating material. The ionexchange material is Li₄Mn₅O₁₂ and the coating material is ZrO₂. Theparticles are comprised of 96 wt. % active material and 4 wt. % of thecoating. The particles have a mean diameter of 30 microns, and thecoating thickness is approximately 100 nm. The particles are created byfirst synthesizing Li₄Mn₅O₁₂ via solid state method and then the coatingis deposited on the surface of the Li₄Mn₅O₁₂ using Zr(IV)-propoxide as aprecursor.

The ion exchange particles are loaded into an ion exchange reactor shownin FIG. 3. The ion exchange reactor comprises a conical tank (301), anexternal settling tank (302) with an inlet taking dilute slurry from thetank and one outlet returning concentrated slurry to the tank andanother outlet removing liquid from the system, an overhead stirrer(303), a pH controller (304), and a spraying system (not shown) at thetop of the tank with one or more nozzles positioned to spray water towash ion exchange particles off the sides of the tank and down to thebottom of the tank.

The particles are loaded into the tank in an aqueous slurry. 1.5N H₂SO₄acid is pumped into the tank to create a slurry with H₂SO₄ at anormality of 0.75N. The acid is stirred with the ion exchange particleto yield Li₂SO₄ in solution. During acid treatment, the particles absorbhydrogen while releasing lithium. The Li₄Mn₅O₁₂ active material isconverted to a protonated state with a hydrogen-enriched composition.The ZrO₂ coating allows diffusion of hydrogen and lithium respectivelyto and from the active material while providing a protective barrierthat limits dissolution of manganese and oxygen from the activematerial. After 40 minutes, the eluate solution is collected from thetank through the settling tank for elemental analysis to measure theeluate composition.

After treatment in acid, the protonated particles are treated with brinewherein the particles absorb lithium while releasing hydrogen. Theparticles are converted from a protonated state to a lithiated statewith a lithium-enriched composition. An aqueous solution of NaOH isadded to the tank to maintain the pH of the brine at 6. After 4 hours,the spent brine is removed from the tank through the settling tank. Theion exchange particles are then washed with water through the sprayingsystem. The particles are washed three times with water, and the wateris drained from the tank through the settling tank, leaving aconcentrated aqueous slurry of the ion exchange particles at the bottomof the tank.

The lithiated material is then treated again with acid to yield lithiumin solution as described previously. The cycle of protonation andlithiation is repeated to extract lithium from the brine and yield aLi₂SO₄ solution.

Example 4: Ion Exchange Reactor with External Settling Tank

Lithium is extracted from a brine using ion exchange particles. Thebrine is an aqueous solution containing 70,000 mg/L Na, 1,000 mg/L Ca,5,000 mg/L Mg, and 200 ppm Li. The ion exchange particles are comprisedof an ion exchange material that is Li₄Mn₅O₁₂. The particles have a meandiameter of 30 microns. The Li₄Mn₅O₁₂ is synthesized via a solid statemethod.

The ion exchange particles are loaded into an ion exchange reactor shownin FIG. 4. The ion exchange reactor comprises a cylindrical tank (401),an external settling tank (402) with an inlet taking dilute slurry fromthe tank and one outlet returning concentrated slurry to the tank andanother outlet removing liquid from the system, an overhead stirrer(403), a pH controller (404), and a spraying system (not shown) at thetop of the tank with one or more nozzles positioned to spray water towash ion exchange particles off the sides of the tank and down to thebottom of the tank.

The particles are loaded into the tank in an aqueous slurry. 1.5N H₂SO₄acid is pumped into the tank to create a slurry with H₂SO₄ at anormality of 0.75N. The acid is stirred with the ion exchange particleto yield Li₂SO₄ in solution. During acid treatment, the particles absorbhydrogen while releasing lithium. The Li₄Mn₅O₁₂ active material isconverted to a protonated state with a hydrogen-enriched composition.After 40 minutes, the eluate solution is collected from the tank throughthe settling tank for elemental analysis to measure the eluatecomposition.

After treatment in acid, the protonated particles are treated with brinewherein the particles absorb lithium while releasing hydrogen. Theparticles are converted from a protonated state to a lithiated statewith a lithium-enriched composition. An aqueous solution of NaOH isadded to the tank to maintain the pH of the brine at 6. After 4 hours,the spent brine is removed from the tank through the settling tank. Theion exchange particles are then washed with water through the sprayingsystem. The particles are washed three times with water, and the wateris drained from the tank through the settling tank, leaving aconcentrated aqueous slurry of the ion exchange particles at the bottomof the tank.

The lithiated material is then treated again with acid to yield lithiumin solution as described previously. The cycle of protonation andlithiation is repeated to extract lithium from the brine and yield aLi₂SO₄ solution.

Example 5: Ion Exchange System with External Filters

Lithium is extracted from a brine using ion exchange particles. Thebrine is an aqueous solution containing 70,000 mg/L Na, 1,000 mg/L Ca,5,000 mg/L Mg, and 200 ppm Li. The ion exchange particles are comprisedof an ion exchange material that is Li₄Mn₅O₁₂. The particles have a meandiameter of 30 microns. The Li₄Mn₅O₁₂ is synthesized via a solid statemethod.

The ion exchange particles are loaded into an ion exchange reactor shownin FIG. 5. The ion exchange reactor comprises a larger cylindrical brinetank for brine mixing and water washing (501), a smaller cylindricalacid tank for acid mixing (502), a settling tank for removing liquidfrom the acid tank (503), a settling tank for removing liquid from thebrine tank (504), and a settling tank for moving the ion exchangeparticles between the acid tank and the brine tank (505) while removingwater to form a more concentrated slurry prior to acid elution. Eachtank is fitted with an overhead stirrer, a pH controller (not shown),and a spraying system (not shown) at the top of the tank with one ormore nozzles positioned to spray water to wash ion exchange particlesoff the sides of the tank and down to the bottom of the tank.

The particles are loaded into the acid tank in an aqueous slurry. 1.5NHCl acid is pumped into the tank to create a slurry with HCl at anormality of 0.75N HCl. The acid is stirred with the ion exchangeparticles to yield LiCl in solution. During acid treatment, theparticles absorb hydrogen while releasing lithium. The Li₄Mn₅O₁₂ activematerial is converted to a protonated state with a hydrogen-enrichedcomposition. After 30 minutes, the slurry of acidic eluate and ionexchange particles is separated into a concentrated slurry and an eluatesolution using an external settling tank (503). The concentrated slurryis reinjected into the acid tank for washing. Then the slurry is washedwith water using the external settling tank (503) to remove a majorityof the water. Then the slurry is transferred to the brine tank using anexternal settling tank (505) while removing some water containingresidual acid.

In the brine tank, the protonated particles are treated with brinewherein the particles absorb lithium while releasing hydrogen. Theparticles are converted from a protonated state to a lithiated statewith a lithium-enriched composition. An aqueous slurry of Ca(OH)₂ isadded to the tank to maintain the pH of the brine at 7. After 6 hours,the spent brine is removed from the tank through the settling tank (504)while the ion exchange particles are returned to the brine tank. The ionexchange particles are then washed with water through the sprayingsystem. The particles are washed three times with water, and the wateris removed using the external settling tank (504) connected to the brinetank, leaving an aqueous slurry of the ion exchange particles at thebottom of the tank. The slurry is then moved to the acid tank through anexternal settling tank (505) while removing excess water to increase theconcentration of the slurry being loaded into the acid tank.

The lithiated material is then treated again with acid to yield lithiumin solution as described previously. The cycle of protonation andlithiation is repeated to extract lithium from the brine and yield aLiCl solution.

Example 6: Ion Exchange System with Multiple Brine Reactors Sharing OneAcid Reactor

Lithium is extracted from a brine using ion exchange particles. Thebrine is an aqueous solution containing 60,000 mg/L Na, 20,000 mg/L Ca,5,000 mg/L Mg, and 120 ppm Li. The ion exchange particles are comprisedof an ion exchange material that is Li₄Mn₅O₁₂. The particles have a meandiameter of 40 microns. The Li₄Mn₅O₁₂ is synthesized via a solid statemethod.

The ion exchange particles are loaded into an ion exchange system shownin FIG. 6. The ion exchange system comprises four brine reactors forbrine mixing and water washing (601, 602, 603, 604) with large conicaltanks incorporating internal candle filters, overhead stirrers, and pHcontrollers; and one acid reactor for acid elution (605) with a smallerconical tank incorporating internal candle filters and an overheadstirrer. Each tank is fitted with a spraying system at the top of thetank with one or more nozzles positioned to spray washing solution towash ion exchange particles off the sides of the tanks and down to thebottom of the tanks while removing soluble species from the tank.

In the brine tanks, the protonated particles are treated with brinewherein the particles absorb lithium while releasing hydrogen. Theparticles are converted from a protonated state to a lithiated statewith a lithium-enriched composition. An aqueous slurry of Ca(OH)₂ isadded to the tank to maintain the pH of the brine at 6.5. The lithiumuptake from brine is staggered in time between the reactors with eachbrine reactor starting lithium uptake approximately two hours after thenext. After each brine reactor has stirred the ion exchange particles inbrine for eight hours, the depleted brine is removed through the candlefilters. Then, the ion exchange particles are washed five times withwater where the water is removed through the candle filters. Then theremaining slurry of water and ion exchange particles is transferred tothe acid reactor.

The particles are loaded into the acid tank in an aqueous slurry. 1.5NHCl acid is pumped into the tank to create a slurry with HCl at anormality of 0.75N. Additional 1.5N HCl acid solution is added to thetank during elution to stimulate further lithium elution from the ionexchange particles. The acid is stirred with the ion exchange particleto yield a LiCl eluate solution. During acid treatment, the particlesabsorb hydrogen while releasing lithium. The Li₄Mn₅O₁₂ active materialis converted to a protonated state with a hydrogen-enriched composition.After 45 minutes, the acid eluate is removed through the candle filtersand sent to an eluate processing unit to form battery-grade lithiumcarbonate. The remaining acidic slurry is washed with water once, andthe water is removed through the candle filters. Then the slurry istransferred to the brine tank. After the slurry has been transferredback to the brine tank, the next brine reactor is washed and the slurryfrom that next brine reactor is transferred to the acid reactor forelution.

Example 7: Continuous Ion Exchange System with Multiple Reactors

Lithium is extracted from a brine using ion exchange particles. Thebrine is an aqueous solution containing 70,000 mg/L Na, 30,000 mg/L Ca,4,000 mg/L Mg, and 80 ppm Li. The ion exchange particles are comprisedof an ion exchange material that is Li₄Mn₅O₁₂. The particles have a meandiameter of 30 microns. The Li₄Mn₅O₁₂ is synthesized via s solid statemethod.

The ion exchange particles are loaded into an ion exchange system shownin FIG. 7. The ion exchange system comprises a brine circuit comprisingfour brine reactors for brine mixing and water washing (701, 702, 703,704) incorporating large conical tanks, external settling tanks,overhead stirrers, and pH controllers; a water washing circuit; and anacid circuit comprising two acid reactors for acid elution (705, 706)incorporating smaller conical tanks, external settling tanks, andoverhead stirrers. Each tank is fitted with a spraying system at the topof the tank with one or more nozzles positioned to spray aqueous washingsolution to wash ion exchange particles off the sides of the tanks anddown to the bottom of the tanks.

In the brine tanks, the protonated particles are treated with brinewherein the particles absorb lithium while releasing hydrogen. Theparticles are converted from a protonated state to a lithiated statewith a lithium-enriched composition. An aqueous slurry of Ca(OH)₂ isadded to the tank to maintain the pH of the brine at 6.5. The brineflows continuously through the series of four brine reactors as the ionexchange particles flow in the counter-current direction. The ionexchange particles move in an aqueous slurry. The brine and ion exchangeparticles are separated using the external settling tanks. The correctrelative velocities of brine and ion exchange particles through thesystem is maintained by reinjecting brine or ion exchange particles backinto a reactor from which they are removed as needed. When the ionexchange particles reach the end of the brine circuit, they aretransferred to a water washing circuit where residual brine is removedfrom the particles. Excess water is removed after washing through afilter to form a concentrated slurry that is transferred to the acidcircuit.

The particles are then transferred into the acid circuit. The particlesmove through the acid circuit while acid solution enters the acidcircuit at the other end of the circuit and moves through the acidcircuit in a counter-current direction. The external settling tanks areusing to separate the ion exchange particles from the acid eluate. 1.5NHCl acid is pumped into the tank where the acid solution enters the acidcircuit to create a slurry with HCl at a normality of 0.75N. The ionexchange particles release lithium into the acid solution to form anacid-eluate solution. The acid-eluate solution is transferred to thenext acid reactor, where the acid-eluate solution is further convertedto an eluate solution. The eluate solution is removed from the acidcircuit and processed to form battery-grade lithium hydroxide viamembrane electrolysis. The ion exchange particles leaving the acidcircuit are washed in a washing circuit and returned to the start of thebrine circuit.

Example 8: Ion Exchange Reactor with Staged Elution

Lithium is extracted from a brine using coated ion exchange particles.The brine is an aqueous solution containing 70,000 mg/L Na, 12,000 mg/LCa, 3,000 mg/L Mg, and 200 ppm Li. The coated ion exchange particles arecomprised of an ion exchange material and a coating material. The ionexchange material is Li₄Mn₅O₁₂ and the coating material is SiO₂. Theparticles are comprised of 94 wt. % active material and 6 wt. % ofcoating material. The particles have a mean diameter of 30 microns, andthe coating thickness is approximately 400 nm. The particles are createdby first synthesizing Li₄Mn₅O₁₂ via a solid state method and then thecoating is deposited on the surface of the Li₄Mn₅O₁₂ using TEOS as aprecursor.

The ion exchange particles are loaded into an ion exchange system shownin FIG. 8. The ion exchange system comprises an ion exchange reactor(801) comprising an array of internal candle filters with PEEK 12 ummesh fitted to a PVC pipe to allow fluid to flow into and out of thetank through the mesh while the ion exchange particles and retainedinside the tank, an overhead stirrer, a pH controller, and a sprayingsystem at the top of the tank with multiple nozzles to spray water towash ion exchange particles off the sides of the tank and down to thebottom of the tank; an acid feed tank (802); and a staged eluate tank(803).

The reactor is operator as described in Example 2, but during elution,the ion exchange particles that are saturated with lithium are firsteluted with an acid-eluate solution that is an approximately 50/50mixture of lithium ions and protons so that the acid-eluate solution isconverted to an eluate solution with 90% lithium ions and only 10%protons, maximizing conversion of the protons to lithium ions. Theeluate solution is removed from the tank and further processed intobattery-grade lithium hydroxide. Then, fresh acid is flowed into thetank, converted to an acid-eluate solution that is an approximately50/50 mixture of lithium ions and protons, and this acid-eluate solutionis then flowed into the stage eluate tank for storage until the nextelution step. The ion exchange particles are washed with water, treatedwith brine with pH controlled at 6.5, washed with water again, and thenreturned to elution as described above.

Example 9: Ion Exchange Reactor

Lithium was extracted from a brine using coated ion exchange particles.The brine was an aqueous solution containing 100,000 mg/L Na and 300 ppmLi. The particles were comprised of 85 wt. % active material and 15 wt.% of coating material. The particles had a mean diameter of 40 microns.

The ion exchange particles were loaded into an ion exchange reactorshown in FIG. 9A. The ion exchange reactor comprised a cone-bottom tank(901), a polyetheretherketone 12 micron pore size mesh mounted at thebottom of the cone-bottom of the tank (902) to allow fluid to be pumpedinto and out of the tank through the mesh while the ion exchangeparticles are retained inside the tank, an overhead stirrer (903), a pHcontroller (904), an internal filter comprising a polyetheretherketone35 micron pore size mesh (905), and a spraying system (not shown) at thetop of the tank with one or more nozzles positioned to spray water towash ion exchange particles off the sides of the tank and down to thebottom of the tank.

The particles were loaded into the tank as a dry material. 2.0 N HClacid was pumped into the tank and stirred with the ion exchange particleto yield a LiCl eluate solution. During acid treatment, the particlesabsorbed hydrogen while releasing lithium. The active material wasconverted to a protonated state with a hydrogen-enriched composition.The coating allowed diffusion of hydrogen and lithium respectively toand from the active material while providing a protective barrier thatprotects the active material. After 40 minutes, the eluate solution wascollected from the tank through the meshes, dewatered, purified usingsodium carbonate precipitation and resin ion exchange beads to removetrace Mg/Ca, and processed into lithium carbonate through addition ofsodium carbonate solution at 90 degrees Celsius.

After treatment in acid, the protonated particles were treated withbrine wherein the particles absorb lithium while releasing hydrogen. Thebrine was pumped into the tank and stirred with the ion exchangeparticles, and the particles are converted from a protonated state to alithiated state with a lithium-enriched composition. An aqueous solutionof NaOH was added to the tank to maintain the pH of the brine at 6.After 4 hours, the spent brine is removed from the tank through themeshes. The ion exchange particles were then washed with water throughthe spraying system. The particles were washed three times with water,and the water was drained from the tank through the meshes, leaving amoist bed of the ion exchange particles at the bottom of the tank withlow water content.

The lithiated material was then treated again with acid to yield lithiumin solution as described previously. The cycle of protonation andlithiation was repeated to extract lithium from the brine and yield aLiCl solution. Degradation of the ion exchange particles was limited dueto the coating providing a protective barrier. FIG. 9B shows lithiumrecovery (the amount of lithium yielded in the LiCl solution as apercentage of the total lithium in the brine) from the brine overmultiple cycles between brine and acid.

Example 10: Ion Exchange Reactor with Attached Column

Lithium is extracted from a brine using coated ion exchange particles.The brine is an aqueous chloride solution containing 100,000 mg/L Na,200 ppm Li, and other species including Ca, Mg, and B. The coated ionexchange particles are comprised of an ion exchange material and acoating material. The ion exchange material is Li₂MnO₃ and the coatingmaterial is titanium dioxide. The particles are comprised of 95 wt. %active material and 5 wt. % of coating material. The particles have amean diameter of 200 microns. The particles are created by firstsynthesizing Li₂MnO₃ via a solid state method and then the coating isdeposited from a Ti-propoxide precursor onto the surface of the Li₂MnO₃material.

The ion exchange particles are loaded into an ion exchange reactor shownin FIG. 10. The ion exchange reactor comprises a cone-bottom tank with athinner cylindrical column connected and mounted at the bottom of thecone-bottom tank (1001), a polypropylene 100 um mesh mounted at thebottom of the column (1002) to allow fluid to be pumped into and out ofthe tank through the mesh while the ion exchange particles are retainedinside the tank, an overhead stirrer (1003), a pH controller (1004), aninternal filter comprising a polypropylene 100 micron pore size mesh(1005), and a spraying system (not shown) at the top of the tank withone or more nozzles positioned to spray water to wash ion exchangeparticles off the sides of the tank and down to the bottom of the tank.

The particles are loaded into the tank as a dry material. 1.5 N sulfuricacid is pumped into the tank and stirred with the ion exchange particleto yield a lithium sulfate eluate solution. During acid treatment, theparticles absorb hydrogen while releasing lithium. The coating allowsdiffusion of hydrogen and lithium respectively to and from the activematerial while providing a protective barrier that protects the activematerial. After 40 minutes, the eluate solution is collected from thetank through the mesh, dewatered, purified using sodium carbonateprecipitation and resin ion exchange beads to remove trace Mg/Ca, andprocessed into lithium carbonate through addition of sodium carbonatesolution at 90 degrees Celsius.

After treatment in acid, the protonated particles are treated with brinewherein the particles absorb lithium while releasing hydrogen. The brineis pumped into the tank and stirred with the ion exchange particles, andthe particles are converted from a protonated state to a lithiated statewith a lithium-enriched composition. An aqueous solution of NaOH isadded to the tank to maintain the pH of the brine at 6. After 4 hours,the spent brine is removed from the tank through the meshes. The ionexchange particles form a settled bed in the column. The ion exchangeparticles are washed continuously with water, which flows through thecolumn to efficiently remove residual brine from the ion exchangeparticles. After washing, the residual wash water is drained from thebottom of the column through the mesh, leaving a moist bed of the ionexchange particles at the bottom of the column with minimal entrainmentof brine and minimal entrainment of water.

The lithiated material is then treated again with acid to yield lithiumin solution as described previously. The cycle of protonation andlithiation is repeated to extract lithium from the brine and yield alithium sulfate solution. Degradation of the ion exchange particles islimited due to the coating providing a protective barrier.

Example 11: Ion Exchange Reactor with Attached Column and FluidizingPump

Lithium is extracted from a brine using ion exchange particles. Thebrine is an aqueous chloride solution containing 60,000 mg/L Ca, 100 ppmLi, and other species including Na, Mg, and B. The coated ion exchangeparticles are comprised of an active ion exchange material and a polymercoating. The particles have a mean diameter of 30 microns.

The ion exchange particles are loaded into an ion exchange reactor shownin FIG. 11. The ion exchange reactor comprises a cone-bottom tank with athinner cylindrical column connected and mounted at the bottom of thecone-bottom tank (1101), a polymer-coated steel mesh with a 5 micronpore size mounted at the bottom of the column (1102) to allow fluid tobe pumped into and out of the tank through the mesh while the ionexchange particles are retained inside the tank, an overhead stirrer(1103), a pH controller (1104), a pumping unit to pump liquid out of thetank and back into the bottom of the column (1105) where the inlets andoutlets of the pumping unit are covered with a polymer-coated steel meshwith a 5 micron pore size, an internal filter comprising apolymer-coated steel mesh with a 5 micron pore size (1106), and aspraying system (not shown) at the top of the tank with one or morenozzles positioned to spray water to wash ion exchange particles off thesides of the tank and down to the bottom of the tank.

The particles are loaded into the tank as a dry material. 1.0 Nhydrochloric acid is pumped into the tank and stirred with the ionexchange particle to yield a lithium chloride eluate solution. Duringacid treatment, the particles absorb hydrogen while releasing lithium.After 10 minutes, the eluate solution is collected from the tank throughthe mesh, dewatered, purified using sodium carbonate precipitation andresin ion exchange beads to remove trace Mg/Ca, and processed intolithium carbonate through addition of sodium carbonate solution at 90degrees Celsius.

After treatment in acid, the protonated particles are treated with brinewherein the particles absorb lithium while releasing hydrogen. The brineis pumped into the tank and stirred with the ion exchange particles.While the tank is stirred, brine is pumped from the tank with thepumping unit and injected at the bottom of the column to fluidize anyparticles that settle in the column and suspend the particles in thebrine which is stirring in the tank. The particles are converted from aprotonated state to a lithiated state with a lithium-enrichedcomposition. An aqueous slurry of Ca(OH)₂ is added to the tank tomaintain the pH of the brine at 6. After 3 hours, the spent brine isremoved from the tank through the meshes. The ion exchange particlesform a settled bed in the column. The ion exchange particles are washedcontinuously with water, which flows through the column to efficientlyremove residual brine from the ion exchange particles. After washing,the residual wash water is drained from the bottom of the column throughthe meshes, leaving a moist bed of the ion exchange particles at thebottom of the column with minimal entrainment of brine and minimalentrainment of water.

The lithiated material is then treated again with acid to yield lithiumin solution as described previously. The cycle of protonation andlithiation is repeated to extract lithium from the brine and yield alithium chloride solution. Degradation of the ion exchange particles islimited due to the coating providing a protective barrier.

Example 12: Ion Exchange Reactor with Fluidizing Pump

Lithium is extracted from a brine using coated ion exchange particles.The brine is an aqueous solution containing 100,000 mg/L Na and 500 ppmLi. The coated ion exchange particles are comprised of an ion exchangematerial and a coating material. The ion exchange material is Li₄Ti₅O₁₂and the coating material is TiO₂. The particles are comprised of 90 wt.% active material and 10 wt. % of coating material. The particles have amean diameter of 80 microns. The particles are created by firstsynthesizing Li₄Ti₅O₁₂ and then the coating is deposited onto thesurface of the Li₄Ti₅O₁₂ material.

The ion exchange particles are loaded into an ion exchange reactor shownin FIG. 12. The ion exchange reactor comprised a cone-bottom tank(1201), a polyetheretherketone 35 micron pore size mesh mounted at thebottom of the cone-bottom of the tank (1202) to allow fluid to be pumpedinto and out of the tank through the mesh while the ion exchangeparticles are retained inside the tank, an overhead stirrer (1203), a pHcontroller (1204), an internal filter comprising a polyetheretherketone35 micron pore size mesh (1206), a pumping unit to pump liquid out ofthe tank and back into the bottom of the tank (1205) where the inletsand outlets of the pumping unit are covered with a polyetheretherketone35 micron pore size mesh, and a spraying system (not shown) at the topof the tank with one or more nozzles positioned to spray water to washion exchange particles off the sides of the tank and down to the bottomof the tank.

The particles are loaded into the tank as a dry material. 1.5 N HCl acidis pumped into the tank and stirred with the ion exchange particle toyield a LiCl eluate solution. During acid treatment, the particlesabsorb hydrogen while releasing lithium. The Li₄Ti₅O₁₂ active materialis converted to a protonated state with a hydrogen-enriched composition.The coating allows diffusion of hydrogen and lithium respectively to andfrom the active material while providing a protective barrier thatprotects the active material. After 15 minutes, the eluate solution iscollected from the tank through the meshes, dewatered, purified usingsodium carbonate precipitation and resin ion exchange beads to removetrace Mg/Ca, and processed into lithium carbonate through addition ofsodium carbonate solution at 90 degrees Celsius.

After treatment in acid, the protonated particles are treated with brinewherein the particles absorb lithium while releasing hydrogen. The brineis pumped into the tank and stirred with the ion exchange particles, andthe particles are converted from a protonated state to a lithiated statewith a lithium-enriched composition. An aqueous solution of NaOH isadded to the tank to maintain the pH of the brine at 6. After 4 hours,the spent brine is removed from the tank through the meshes. The ionexchange particles are then washed with water through the sprayingsystem. The particles are washed three times with water, and the wateris drained from the tank through the meshes, leaving a moist bed of theion exchange particles at the bottom of the tank with low water content.

The lithiated material is then treated again with acid to yield lithiumin solution as described previously. The cycle of protonation andlithiation is repeated to extract lithium from the brine and yield aLiCl solution. Degradation of the ion exchange particles is limited dueto the coating providing a protective barrier. While preferredembodiments of the present invention have been shown and describedherein, it will be obvious to those skilled in the art that suchembodiments are provided by way of example only. Numerous variations,changes, and substitutions will now occur to those skilled in the artwithout departing from the invention. It should be understood thatvarious alternatives to the embodiments of the invention describedherein is optionally employed in practicing the invention. It isintended that the following claims define the scope of the invention andthat methods and structures within the scope of these claims and theirequivalents be covered thereby.

What is claimed is:
 1. An ion exchange reactor for generating a lithiumeluate solution from a liquid resource, comprising: a) a tank; b) ionexchange particles that selectively absorb lithium from said liquidresource and elute said lithium eluate solution when treated with anacid solution after absorbing lithium from said liquid resource; c) oneor more particle traps; and d) provision to modulate pH of said liquidresource.
 2. The ion exchange reactor of claim 1, wherein said tank hasa conical shape.
 3. The ion exchange reactor of claim 2, wherein saidconical shape allows said ion exchange particles to settle into asettled bed so that liquid can be removed from above said settled bed.4. The ion exchange reactor according to any one of claims 1-3, whereinmodulation of said pH of said liquid resource occurs in the tank.
 5. Theion exchange reactor according to any one of claims 1-3, whereinmodulation of said pH of said liquid resource occurs prior to injectionof said liquid resource into the tank.
 6. The ion exchange reactor ofclaim 1, wherein said one or more particle traps comprise one or morefilters inside said tank.
 7. The ion exchange reactor according to anyone of claims 1-6, wherein said one or more particle traps is located atthe bottom of said tank.
 8. The ion exchange reactor according to anyone of claims 1-7, wherein said one or more particle traps comprise oneor more meshes.
 9. The ion exchange reactor according to any one ofclaims 1-8, wherein said one or more meshes comprise a pore space ofless than about 200 microns.
 10. The ion exchange reactor according toany one of claims 1-8, wherein said one or more meshes comprise a porespace of less than about 100 microns.
 11. The ion exchange reactoraccording to any one of claims 1-8, wherein said one or more meshescomprise a pore space of less than about 100 microns.
 12. The ionexchange reactor according to any one of claims 1-8, wherein said one ormore meshes comprise a pore space of less than about 50 microns.
 13. Theion exchange reactor according to any one of claims 1-8, wherein saidone or more meshes comprise a pore space of less than about 25 microns.14. The ion exchange reactor according to any one of claims 1-8, whereinsaid one or more meshes comprise a pore space of less than about 10microns.
 15. The ion exchange reactor according to any one of claims1-14, wherein said one or more particle traps comprise multi-layeredmeshes.
 16. The ion exchange reactor according to any one of claims1-15, wherein said multi-layered meshes comprise at least one finer meshfor filtration and at least one coarser mesh for structural support. 17.The ion exchange reactor according to any one of claims 1-16, whereinsaid one or more particle traps comprise one or more meshes supported bya structural support.
 18. The ion exchange reactor according to any oneof claims 1-17, wherein said one or more particle traps comprise one ormore polymer meshes.
 19. The ion exchange reactor according claim 18,wherein said one or more polymer meshes are selected from the groupconsisting of polyetheretherketone, ethylene tetrafluorethylene,polyethylene terephthalate, polypropylene, and combinations thereof. 20.The ion exchange reactor according to any one of claims 1-17, whereinsaid one or more particle traps comprise one or more meshes comprising ametal wire mesh.
 21. The ion exchange reactor according to claim 20,wherein said metal wire mesh is coated with a polymer.
 22. The ionexchange reactor according to any one of claims 1-21, wherein said ionexchange reactor is configured to move said ion exchange particles intoone or more columns for washing.
 23. The ion exchange reactor accordingto claim 22, wherein said ion exchange reactor is configured to allowthe ion exchange particles to settle into one or more columns forwashing.
 24. The ion exchange reactor according to claim 23, whereinsaid columns are affixed to the bottom of said tank.
 25. The ionexchange reactor according to any one of claims 1-24, wherein said oneor more particle traps comprise one or more filters mounted in one ormore ports through the wall of said tank.
 26. The ion exchange reactoraccording to any one of claims 1-24, wherein said one or more particletraps comprise one or more filters external to said tank, and withprovision for fluid communication between said one or more filters andsaid tank.
 27. The ion exchange reactor according to any one of claims1-24, wherein said one or more particle traps comprise one or moregravity sedimentation devices external to said tank, and with provisionfor fluid communication between said one or more gravity sedimentationdevices and said tank.
 28. The ion exchange reactor according to any oneof claims 1-24, wherein said one or more particle traps comprise one ormore gravity sedimentation devices internal to said tank.
 29. The ionexchange reactor according to any one of claims 1-24, wherein said oneor more particle traps comprise one or more centrifugal sedimentationdevices external to said tank, and with provision for fluidcommunication between said one or more centrifugal sedimentation devicesand said tank.
 30. The ion exchange reactor according to any one ofclaims 1-24, wherein said one or more particle traps comprise one ormore centrifugal sedimentation devices internal to said tank.
 31. Theion exchange reactor according to any one of claims 1-24, wherein saidone or more particle traps comprise one or more settling tanks, one ormore centrifugal devices, or combinations thereof external to said tank,and with provision for fluid communication between said one or moresettling tanks, centrifugal devices, or combinations thereof, and saidtank.
 32. The ion exchange reactor according to any one of claims 1-24,wherein said one or more particle traps comprise one or more meshes, oneor more centrifugal devices, or combinations thereof external to saidtank, and with provision for fluid communication between said one ormore meshes, centrifugal devices, or combinations thereof, and saidtank.
 33. The ion exchange reactor according to any one of claims 1-24,wherein said one or more particle traps comprise one or more settlingtanks, one or more meshes, or combinations thereof external to saidtank, and with provision for fluid communication between said one ormore settling tanks, meshes, or combinations thereof, and said tank. 34.The ion exchange reactor according to any one of claims 1-24, whereinsaid one or more particle traps comprise one or more meshes, one or moresettling tanks, one or more centrifugal devices, or combinations thereofexternal to said tank, and with provision for fluid communicationbetween said one or more meshes, one or more settling tanks, centrifugaldevices, or combinations thereof, and said tank.
 35. The ion exchangereactor according to any one of claims 1-34, wherein the ion exchangeparticles are stirred.
 36. The ion exchange reactor of claim 35, whereinthe ion exchange particles are stirred by a mixer.
 37. The ion exchangereactor of claim 35, wherein the ion exchange particles are stirred by apropeller.
 38. The ion exchange reactor according to any one of claims1-37, wherein the ion exchange particles are fluidized by pumpingsolution into the tank near the bottom of the tank.
 39. The ion exchangereactor according to any one of claims 1-37, wherein the ion exchangeparticles are fluidized by pumping solution from the tank back into thetank near the bottom of the tank.
 40. The ion exchange reactor accordingto any one of claims 1-37, wherein the ion exchange particles arefluidized by pumping a slurry of the ion exchange particles from nearthe bottom of the tank to a higher level in the tank.
 41. The ionexchange reactor according to any one of claims 1-40, further comprisingone or more staged elution tanks, wherein intermediate eluate solutionscomprising mixtures of protons and lithium ions are stored and usedfurther to elute lithium from said ion exchange particles that arefreshly lithiated.
 42. The ion exchange reactor according to any one ofclaims 1-40, further comprising one or more staged elution tanks,wherein intermediate eluate solutions comprising mixtures of protons andlithium ions are mixed with additional acid and used further to elutelithium from said ion exchange particles.
 43. The ion exchange reactoraccording to any one of claims 1-42, wherein said ion exchange particlesfurther comprise a coating material.
 44. The ion exchange reactor ofclaim 43, wherein said coating material is a polymer.
 45. The ionexchange reactor of claim 44, wherein said coating of said coatingmaterial comprises a chloro-polymer, a fluoro-polymer, achloro-fluoro-polymer, a hydrophilic polymer, a hydrophobic polymer,co-polymers thereof, mixtures thereof, or combinations thereof.
 46. Anion exchange system for generating a lithium eluate solution from aliquid resource, comprising: a. a networked plurality of tanks; b. ionexchange particles that selectively absorb lithium from said liquidresource and elute said lithium eluate solution when treated with anacid solution; c. one or more particle traps; and d. provision tomodulate pH of said liquid resource.
 47. The ion exchange system ofclaim 46, wherein said ion exchange particles are retained in saidnetworked plurality of tanks with flows of brine, washing solution, andacid alternately moving through said plurality of tanks.
 48. The ionexchange system of claim 46, wherein said ion exchange particles aremoved through said networked plurality of tanks against counter-currentflows of brine, washing solution, and acid.
 49. The ion exchange systemof claim 46, wherein tanks selected from said networked plurality oftanks are sized for batches of brine, washing solution, or acid andwherein said ion exchange particles are moved through said networkedplurality of tanks.
 50. A method of generating a lithium eluate solutionfrom a liquid resource, comprising: a. providing an ion exchange reactorcomprising a tank, ion exchange particles that selectively absorblithium from a liquid resource and elute a lithium eluate solution whentreated with an acid solution after absorbing lithium ions from saidliquid resource, one or more particle traps, and provision to modulatepH of said liquid resource; b. flowing a liquid resource into said ionexchange reactor thereby allowing said ion exchange particles toselectively absorb lithium from said liquid resource; c. treating saidion exchange particles with an acid solution to yield said lithiumeluate solution; and d. passing said lithium eluate solution throughsaid one or more particle traps to collect said lithium eluate solution.51. The method of claim 50, wherein said tank has a conical shape. 52.The method of claim 51, wherein said conical shape allows said ionexchange particles to settle into a settled bed so that liquid can beremoved from above said settled bed.
 53. The method of any one of claims50-52, wherein modulation of said pH of said liquid resource occurs inthe tank.
 54. The method of any one of claims 50-52, wherein modulationof said pH of said liquid resource occurs prior to injection of saidliquid resource into the tank.
 55. The method of claim 50, wherein saidone or more particle traps comprise one or more filters inside saidtank.
 56. The method of any one of claims 50-55, wherein said one ormore particle traps is located at the bottom of said tank.
 57. Themethod of any one of claims 50-56, wherein said one or more particletraps comprise one or more meshes.
 58. The method of any one of claims50-57, wherein said one or more meshes comprise a pore space of lessthan about 200 microns.
 59. The method of any one of claims 50-57,wherein said one or more meshes comprise a pore space of less than about100 microns.
 60. The method of any one of claims 50-57, wherein said oneor more meshes comprise a pore space of less than about 100 microns. 61.The method of any one of claims 50-57, wherein said one or more meshescomprise a pore space of less than about 50 microns.
 62. The method ofany one of claims 50-57, wherein said one or more meshes comprise a porespace of less than about 25 microns.
 63. The method of any one of claims50-57, wherein said one or more meshes comprise a pore space of lessthan about 10 microns.
 64. The method of any one of claims 50-63,wherein said one or more particle traps comprise multi-layered meshes.65. The method of any one of claims 50-64, wherein said multi-layeredmeshes comprise at least one finer mesh for filtration and at least onecoarser mesh for structural support.
 66. The method of any one of claims50-65, wherein said one or more particle traps comprise one or moremeshes supported by a structural support.
 67. The method of any one ofclaims 50-66, wherein said one or more particle traps comprise one ormore polymer meshes.
 68. The method of claim 67, wherein said one ormore polymer meshes are selected from the group consisting ofpolyetheretherketone, ethylene tetrafluorethylene, polyethyleneterephthalate, polypropylene, and combinations thereof.
 69. The methodof any one of claims 50-66, wherein said one or more particle trapscomprise one or more meshes comprising a metal wire mesh.
 70. The methodof claim 69, wherein said metal wire mesh is coated with a polymer. 71.The method of any one of claims 50-70, wherein said ion exchange reactoris configured to move said ion exchange particles into one or morecolumns for washing.
 72. The method of claim 71, wherein said ionexchange reactor is configured to allow the ion exchange particles tosettle into one or more columns for washing.
 73. The method of claim 72,wherein said columns are affixed to the bottom of said tank.
 74. Themethod of any one of claims 50-73, wherein said one or more particletraps comprise one or more filters mounted in one or more ports throughthe wall of said tank.
 75. The method of any one of claims 50-73,wherein said one or more particle traps comprise one or more filtersexternal to said tank, and with provision for fluid communicationbetween said one or more filters and said tank.
 76. The method of anyone of claims 50-73, wherein said one or more particle traps compriseone or more gravity sedimentation devices external to said tank, andwith provision for fluid communication between said one or more gravitysedimentation devices and said tank.
 77. The method of any one of claims50-73, wherein said one or more particle traps comprise one or moregravity sedimentation devices internal to said tank.
 78. The method ofany one of claims 50-73, wherein said one or more particle trapscomprise one or more centrifugal sedimentation devices external to saidtank, and with provision for fluid communication between said one ormore centrifugal sedimentation devices and said tank.
 79. The method ofany one of claims 50-73, wherein said one or more particle trapscomprise one or more centrifugal sedimentation devices internal to saidtank.
 80. The method of any one of claims 50-73, wherein said one ormore particle traps comprise one or more settling tanks, one or morecentrifugal devices, or combinations thereof external to said tank, andwith provision for fluid communication between said one or more settlingtanks, centrifugal devices, or combinations thereof, and said tank. 81.The method of any one of claims 50-73, wherein said one or more particletraps comprise one or more meshes, one or more centrifugal devices, orcombinations thereof external to said tank, and with provision for fluidcommunication between said one or more meshes, centrifugal devices, orcombinations thereof, and said tank.
 82. The method of any one of claims50-73, wherein said one or more particle traps comprise one or moresettling tanks, one or more meshes, or combinations thereof external tosaid tank, and with provision for fluid communication between said oneor more settling tanks, meshes, or combinations thereof, and said tank.83. The method of any one of claims 50-73, wherein said one or moreparticle traps comprise one or more meshes, one or more settling tanks,one or more centrifugal devices, or combinations thereof external tosaid tank, and with provision for fluid communication between said oneor more meshes, one or more settling tanks, centrifugal devices, orcombinations thereof, and said tank.
 84. The method of any one of claims50-83, wherein the ion exchange particles are stirred.
 85. The method ofclaim 84, wherein the ion exchange particles are stirred by a mixer. 86.The method of claim 84, wherein the ion exchange particles are stirredby a propeller.
 87. The method of any one of claims 50-86, wherein theion exchange particles are fluidized by pumping solution into the tanknear the bottom of the tank.
 88. The method of any one of claims 50-86,wherein the ion exchange particles are fluidized by pumping solutionfrom the tank back into the tank near the bottom of the tank.
 89. Themethod of any one of claims 50-86, wherein the ion exchange particlesare fluidized by pumping a slurry of the ion exchange particles fromnear the bottom of the tank to a higher level in the tank.
 90. Themethod of any one of claims 50-89, further comprising one or more stagedelution tanks, wherein intermediate eluate solutions comprising mixturesof protons and lithium ions are stored and used further to elute lithiumfrom said ion exchange particles that are freshly lithiated.
 91. Themethod of any one of claims 50-89, further comprising one or more stagedelution tanks, wherein intermediate eluate solutions comprising mixturesof protons and lithium ions are mixed with additional acid and usedfurther to elute lithium from said ion exchange particles.
 92. Themethod of any one of claims 50-91, wherein said ion exchange particlesfurther comprise a coating material.
 93. The method of claim 92, whereinsaid coating material is a polymer.
 94. The method of claim 93, whereinsaid coating of said coating material comprises a chloro-polymer, afluoro-polymer, a chloro-fluoro-polymer, a hydrophilic polymer, ahydrophobic polymer, co-polymers thereof, mixtures thereof, orcombinations thereof.
 95. An ion exchange reactor for generating alithium eluate solution from a liquid resource, comprising: a) a tankwith a conical shape, wherein said conical shape allows said ionexchange particles to settle into a settled bed so that liquid can beremoved from above said settled bed; b) ion exchange particles thatselectively absorb lithium from said liquid resource and elute saidlithium eluate solution when treated with an acid solution afterabsorbing lithium from said liquid resource; c) one or more particletraps located at the bottom of said tank, wherein said one or moreparticle traps comprise one or more meshes; and d) provision to modulatepH of said liquid resource, wherein said modulation of said pH of saidliquid resource is configured to occur in the tank or prior to injectionof said liquid resource into the tank.
 96. The ion exchange reactor ofclaim 95, wherein said one or more meshes comprise a pore space of lessthan about 200 microns.
 97. The ion exchange reactor of claim 95,wherein said one or more meshes comprise a pore space of less than about100 microns.
 98. The ion exchange reactor of claim 95, wherein said oneor more meshes comprise a pore space of less than about 100 microns. 99.The ion exchange reactor of claim 95, wherein said one or more meshescomprise a pore space of less than about 50 microns.
 100. The ionexchange reactor of claim 95, wherein said one or more meshes comprise apore space of less than about 25 microns.
 101. The ion exchange reactorof claim 95, wherein said one or more meshes comprise a pore space ofless than about 10 microns.
 102. The ion exchange reactor of any one ofclaims 95-101, wherein said one or more meshes are one or more polymermeshes.
 103. The ion exchange reactor of claim 102, wherein said one ormore polymer meshes are selected from the group consisting ofpolyetheretherketone, ethylene tetrafluorethylene, polyethyleneterephthalate, polypropylene, and combinations thereof.
 104. The ionexchange reactor of any one of claims 95-101, wherein said one or moremeshes comprise a metal wire mesh.
 105. The ion exchange reactor ofclaim 104, wherein said metal wire mesh is coated with a polymer. 106.The ion exchange reactor of claim 105, wherein said polymer coating saidmetal wire mesh is selected from the group consisting ofpolyetheretherketone, ethylene tetrafluorethylene, polyethyleneterephthalate, polypropylene, and combinations thereof.
 107. An ionexchange reactor for generating a lithium eluate solution from a liquidresource, comprising: a) a tank with a conical shape, wherein saidconical shape allows said ion exchange particles to settle into asettled bed so that liquid can be removed from above said settled bed;b) ion exchange particles that selectively absorb lithium from saidliquid resource and elute said lithium eluate solution when treated withan acid solution after absorbing lithium from said liquid resource; c)one or more particle traps located at the bottom of said tank, whereinsaid one or more particle traps comprise multi-layered meshes; and d)provision to modulate pH of said liquid resource, wherein saidmodulation of said pH of said liquid resource is configured to occur inthe tank or prior to injection of said liquid resource into the tank.108. The ion exchange reactor of claim 107, wherein said multi-layeredmeshes comprise at least one finer mesh for filtration and at least onecoarser mesh for structural support.
 109. The ion exchange reactor ofclaim 107, wherein said one or more particle traps comprise one or moremeshes supported by a structural support.
 110. The ion exchange reactorof any one of claims 107-109, wherein said one or more meshes are one ormore polymer meshes.
 111. The ion exchange reactor of claim 110, whereinsaid one or more polymer meshes are selected from the group consistingof polyetheretherketone, ethylene tetrafluorethylene, polyethyleneterephthalate, polypropylene, and combinations thereof.
 112. The ionexchange reactor of any one of claims 107-109, wherein said one or moremeshes comprise a metal wire mesh.
 113. The ion exchange reactor ofclaim 112, wherein said metal wire mesh is coated with a polymer. 114.The ion exchange reactor of claim 113, wherein said polymer coating saidmetal wire mesh is selected from the group consisting ofpolyetheretherketone, ethylene tetrafluorethylene, polyethyleneterephthalate, polypropylene, and combinations thereof.
 115. A method ofgenerating a lithium eluate solution from a liquid resource, comprising:a) providing an ion exchange reactor comprising (i) a tank with aconical shape, wherein said conical shape allows said ion exchangeparticles to settle into a settled bed so that liquid can be removedfrom above said settled bed; (ii) ion exchange particles thatselectively absorb lithium from said liquid resource and elute saidlithium eluate solution when treated with an acid solution afterabsorbing lithium from said liquid resource; (iii) one or more particletraps located at the bottom of said tank, wherein said one or moreparticle traps comprise one or more meshes; and (iv) provision tomodulate pH of said liquid resource, wherein said modulation of said pHof said liquid resource is configured to occur in the tank or prior toinjection of said liquid resource into the tank; b) flowing a liquidresource into said ion exchange reactor thereby allowing said ionexchange particles to selectively absorb lithium from said liquidresource; c) treating said ion exchange particles with an acid solutionto yield said lithium eluate solution; and d) passing said lithiumeluate solution through said one or more particle traps to collect saidlithium eluate solution.
 116. The method of claim 115, wherein said oneor more meshes comprise a pore space of less than about 200 microns.117. The method of claim 115, wherein said one or more meshes comprise apore space of less than about 100 microns.
 118. The method of claim 115,wherein said one or more meshes comprise a pore space of less than about100 microns.
 119. The method of claim 115, wherein said one or moremeshes comprise a pore space of less than about 50 microns.
 120. Themethod of claim 115, wherein said one or more meshes comprise a porespace of less than about 25 microns.
 121. The method of claim 115,wherein said one or more meshes comprise a pore space of less than about10 microns.
 122. The method of any one of claims 115-121, wherein saidone or more meshes are one or more polymer meshes.
 123. The method ofclaim 122, wherein said one or more polymer meshes are selected from thegroup consisting of polyetheretherketone, ethylene tetrafluorethylene,polyethylene terephthalate, polypropylene, and combinations thereof.124. The method of any one of claims 115-121, wherein said one or moremeshes comprise a metal wire mesh.
 125. The method of claim 124, whereinsaid metal wire mesh is coated with a polymer.
 126. The method of claim125, wherein said polymer coating said metal wire mesh is selected fromthe group consisting of polyetheretherketone, ethylenetetrafluorethylene, polyethylene terephthalate, polypropylene, andcombinations thereof.
 127. A method of generating a lithium eluatesolution from a liquid resource, comprising: a) providing an ionexchange reactor comprising: (i) a tank with a conical shape, whereinsaid conical shape allows said ion exchange particles to settle into asettled bed so that liquid can be removed from above said settled bed;(ii) ion exchange particles that selectively absorb lithium from saidliquid resource and elute said lithium eluate solution when treated withan acid solution after absorbing lithium from said liquid resource;(iii) one or more particle traps located at the bottom of said tank,wherein said one or more particle traps comprise multi-layered meshes;and (iv) provision to modulate pH of said liquid resource, wherein saidmodulation of said pH of said liquid resource is configured to occur inthe tank or prior to injection of said liquid resource into the tank; b)flowing a liquid resource into said ion exchange reactor therebyallowing said ion exchange particles to selectively absorb lithium fromsaid liquid resource; c) treating said ion exchange particles with anacid solution to yield said lithium eluate solution; and d) passing saidlithium eluate solution through said one or more particle traps tocollect said lithium eluate solution.
 128. The method of claim 127,wherein said multi-layered meshes comprise at least one finer mesh forfiltration and at least one coarser mesh for structural support. 129.The method of claim 127, wherein said one or more particle trapscomprise one or more meshes supported by a structural support.
 130. Themethod of any one of claims 127-129, wherein said one or more meshes areone or more polymer meshes.
 131. The method of claim 130, wherein saidone or more polymer meshes are selected from the group consisting ofpolyetheretherketone, ethylene tetrafluorethylene, polyethyleneterephthalate, polypropylene, and combinations thereof.
 132. The methodof any one of claims 127-129, wherein said one or more meshes comprise ametal wire mesh.
 133. The method of claim 132, wherein said metal wiremesh is coated with a polymer.
 134. The method of claim 133, whereinsaid polymer coating said metal wire mesh is selected from the groupconsisting of polyetheretherketone, ethylene tetrafluorethylene,polyethylene terephthalate, polypropylene, and combinations thereof.